Silicon compound

ABSTRACT

A silicon compound represented by Formula (1). In Formula (1), R 1  is a group independently selected respectively from the group consisting of a hydrogen atom, alkyl, substituted or non-substituted aryl and substituted or non-substituted arylalkyl, and A 1  is an organic group substituted with a halogenated sulfonyl group and is preferably a group represented by Formula (2). In Formula (2), X is halogen; R 2  is alkyl; a is an integer of 0 to 2; and Z 1  is a single bond or alkylene having a carbon number of 1 to 10. 
     
       
         
         
             
             
         
       
     
     The silicon compound provided by the present invention is a silsesquioxane derivative having an excellent living polymerizable radical polymerization initiating function. For example, it is possible to commence polymerization by allowing an acryl base monomer to coexist to form an acryl base polymer making use of one point of the structure of the silsesquioxane in the present invention as a starting point. Because a halogenated sulfonyl group has a strong electrophilicity, it is possible to synthesize various silsesquioxane derivatives by reacting the silicon compound provided by the present invention with various nucleophilic reagents, and it can actively be used as an intermediate useful for organic synthesis.

FIELD OF THE INVENTION

The present invention relates to a novel silicon compound characterizedby having a polymerization initiating ability toward polymerizablemonomers and a polymer obtained using the same.

BACKGROUND OF THE INVENTION

Macromolecular compounds have come to be used in various fields not onlyas a general purpose structure-forming material but also as a valueadded type material having high function and performance, and theimportance of producing polymeric materials under precise design isincreasing. Also in an organic-inorganic composite material containingsilsesquioxane as an inorganic component, it is very important to createa novel functional polymeric material. Such material is obtained bysynthesizing a macromolecular compound having a clear structure andprecisely analyzing a molecular property thereof and a property as anaggregate respectively to thereby make correlation between both clearand setting it as a design guideline. However, conventionalorganic-inorganic composite materials do not necessarily contain apolymer which is controlled in a structure as an organic component, anda lot of them is obtained by mechanically blending silsesquioxane withorganic polymers, so that it used to be very difficult to control thestructure of composite materials as molecular assemblies.

DISCLOSURE OF THE INVENTION

An object of the present invention is to solve the problems describedabove regarding conventional organic-inorganic composite materials byproviding a novel silicon compound characterized by having a livingradical polymerization initiating ability toward polymerizable monomersand a polymer obtained using the same.

The problems described above can be solved by the present inventioncomprising the following structures.

[1] A silicon compound represented by Formula (1):

in Formula (1), seven R¹'s are groups independently selectedrespectively from the group consisting of hydrogen, alkyl, substitutedor non-substituted aryl and substituted or non-substituted arylalkyl; A¹is an organic group substituted with a halogenated sulfonyl group; inthis alkyl, optional hydrogen may be substituted with fluorine, andoptional —CH₂— may be substituted with —O—, —CH═CH—, cycloalkylene orcycloalkenylene; and in alkylene in this arylalkyl, optional hydrogenmay be substituted with fluorine, and optional —CH₂— may be substitutedwith —O— or —CH═CH—.[2] The silicon compound as described in the item [1], wherein sevenR¹'s in Formula (1) are groups independently selected respectively fromthe group consisting of hydrogen, alkyl having a carbon number of 1 to45, substituted or non-substituted aryl and substituted ornon-substituted arylalkyl; in this alkyl having a carbon number of 1 to45, optional hydrogen may be substituted with fluorine, and optional—CH₂— may be substituted with —O—, —CH═CH—, cycloalkylene orcycloalkenylene; andin alkylene in this arylalkyl, optional hydrogen may be substituted withfluorine, and optional —CH₂— may be substituted with —O— or —CH═CH—.[3] The silicon compound as described in the item [1], wherein sevenR¹'s in Formula (1) are groups independently selected respectively fromthe group consisting of hydrogen and alkyl having a carbon number of 1to 30; andin the alkyl having a carbon number of 1 to 30, optional hydrogen may besubstituted with fluorine, and optional —CH₂— may be substituted with—O— or cycloalkylene.[4] The silicon compound as described in the item [1], wherein sevenR¹'s in Formula (1) are groups independently selected respectively fromthe group consisting of alkenyl having a carbon number of 1 to 20 and agroup in which optional —CH₂— is substituted with cycloalkenylene inalkyl having a carbon number of 1 to 20;in the alkenyl having a carbon number of 1 to 20, optional hydrogen maybe substituted with fluorine, and optional —CH₂— may be substituted with—O— or cycloalkylene; andin the group in which optional —CH₂— is substituted with cycloalkenylenein alkyl having a carbon number of 1 to 20, optional hydrogen may besubstituted with fluorine.[5] The silicon compound as described in the item [1], wherein sevenR¹'s in Formula (1) are groups independently selected respectively fromthe group consisting of naphthyl and phenyl in which optional hydrogenmay be substituted with halogen or alkyl having a carbon number of 1 to10;in the alkyl having a carbon number of 1 to 10, optional hydrogen may besubstituted with fluorine, and optional —CH₂— may be substituted with—O—, —CH═CH—, cycloalkylene or phenylene.[6] The silicon compound as described in the item [1], wherein sevenR¹'s in Formula (1) are groups independently selected respectively fromthe group consisting of phenylalkyls in which optional hydrogen on abenzene ring may be substituted with halogen or alkyl having a carbonnumber of 1 to 12; in this alkyl having a carbon number of 1 to 12,optional hydrogen may be substituted with fluorine, and optional —CH₂—may be substituted with —O—, —CH═CH—, cycloalkylene or phenylene; andin alkylene in the phenylalkyl, which has a carbon number of 1 to 12,optional hydrogen may be substituted with fluorine, and optional —CH₂—may be substituted with —O— or —CH═CH—.[7] The silicon compound as described in the item [1], wherein sevenR¹'s in Formula (1) are groups independently selected respectively fromthe group consisting of alkyl having a carbon number of 1 to 8, phenyl,non-substituted naphthyl and phenylalkyl;in the alkyl having 1 to 8 carbon atoms, optional hydrogen may besubstituted with fluorine, and optional —CH₂— may be substituted with—O—, —CH═CH—, cycloalkylene or cycloalkenylene;in the phenyl, optional hydrogen may be substituted with halogen, methylor methoxy; in phenyl in the phenylalkyl, optional hydrogen may besubstituted with fluorine, alkyl having a carbon number of 1 to 4,ethenyl or methoxy; and in alkylene in the phenylalkyl, it has a carbonnumber of 1 to 8, and optional —CH₂— may be substituted with —O— or—CH═CH—.[8] The silicon compound as described in the item [1], wherein sevenR¹'s in Formula (1) are one group selected from the group consisting ofalkyl having a carbon number of 1 to 8, phenyl, non-substituted naphthyland phenylalkyl;in the alkyl having a carbon number of 1 to 8, optional hydrogen may besubstituted with fluorine, and optional —CH₂— may be substituted with—O—, —CH═CH—, cycloalkylene or cycloalkenylene;in the phenyl, optional hydrogen may be substituted with halogen, methylor methoxy;in phenyl in the phenylalkyl, optional hydrogen may be substituted withfluorine, alkyl having a carbon number of 1 to 4, ethenyl or methoxy;andin alkylene in the phenylalkyl, it has a carbon number of 1 to 8, andoptional —CH₂— may be substituted with —O— or —CH═CH—.[9] The silicon compound as described in the item [1], wherein sevenR¹'s in Formula (1) are one group selected from the group consisting ofphenyl, naphthyl and phenylalkyl; in the phenyl, optional hydrogen maybe substituted with halogen, methyl or methoxy;in phenyl in the phenylalkyl, optional hydrogen may be substituted withfluorine, alkyl having a carbon number of 1 to 4, ethenyl or methoxy;andin alkylene in the phenylalkyl, a carbon number thereof is 1 to 8, andoptional —CH₂— may be substituted with —O—.[10] The silicon compound as described in the item [1], wherein sevenR¹'s in Formula (1) are ethyl, 2-methylpropyl, 2,4,4-trimethylpentyl,3,3,3-trifluoropropyl, cyclopentyl, cyclohexyl or non-substitutedphenyl.[11] The silicon compound as described in the item [1], wherein sevenR¹'s in Formula (1) are non-substituted phenyl.[12] The silicon compound as described in any of the items [1] to [11],wherein A¹ in Formula (1) described in the item [1] is a grouprepresented by Formula (2):

in Formula (2), X is halogen; R² is alkyl having a carbon number of 1 to3; a is an integer of 0 to 2; Z¹ is a single bond or alkylene having acarbon number of 1 to 10; in this alkylene having a carbon number of 1to 10, optional —CH₂— may be substituted with —O—, —COO— or —OCO—; andboth of the bonding positions of halogenated sulfonyl and R² on abenzene ring are optional positions.[13] The silicon compound as described in the item [12], wherein Z¹ inFormula (2) is Z²—C₂H₄—; Z² is a single bond or alkylene having a carbonnumber of 1 to 8, and optional —CH₂— in this alkylene may be substitutedwith —O—, —COO— or —OCO—.[14] The silicon compound as described in the item [12], wherein inFormula (2), Z¹ is —C₂H₄—; X is chlorine or bromine; and a is 0.[15] A production process for the silicon compound represented byFormula (1) as described in the item [1], characterized by reacting acompound represented by Formula (3) with trichlorosilane having ahalogenated sulfonyl group:

in Formula (3), seven R¹'s are groups independently selectedrespectively from the group consisting of hydrogen, alkyl, substitutedor non-substituted aryl and substituted or non-substituted arylalkyl; inthis alkyl, optional hydrogen may be substituted with fluorine, andoptional —CH₂— may be substituted with —O—, —CH═CH—, cycloalkylene orcycloalkenylene; and in alkylene in the arylalkyl, optional hydrogen maybe substituted with fluorine, and optional —CH₂— may be substituted with—O— or —CR═CR—.[16] A production process for a silicon compound represented by Formula(5), characterized by reacting a compound represented by Formula (3)with a compound represented by Formula (4):

wherein R¹ in Formula (3) is one group selected from the groupconsisting of alkyl having a carbon number of 1 to 8, phenyl,non-substituted naphthyl and phenylalkyl; in the alkyl having a carbonnumber of 1 to 8, optional hydrogen may be substituted with fluorine,and optional —CH₂— may be substituted with —O—, —CH═CH—, cycloalkyleneor cycloalkenylene; optional hydrogen in the phenyl may be substitutedwith halogen, methyl or methoxy; in the phenylalkyl, optional hydrogenon a benzene ring may be substituted with fluorine, alkyl having acarbon number of 1 to 4, ethenyl or methoxy, and optional —CH₂— inalkylene may be substituted with —O—; R¹ in Formula (5) has the samemeaning as that of R¹ in Formula (3);in Formula (4), X is halogen; R² is alkyl having a carbon number of 1 to3; a is an integer of 0 to 2; Z² is a single bond or alkylene having 1to 8 carbon atoms; in the alkylene having a carbon number of 1 to 8,optional —CH₂— may be substituted with —O—, —COO— or —OCO—; both of thebonding positions of halogenated sulfonyl and R² on a benzene ring areoptional positions; and the meanings of X, R², and Z² in Formula (5) andthe bonding positions of halogenated sulfonyl and R² on a benzene ringeach are the same as those in Formula (4).[17] A production process for the silicon compound represented byFormula (1) as described in the item [1], characterized by reacting acompound represented by Formula (6) with trichlorosilane having ahalogenated sulfonyl group:

in Formula (6), seven R¹'s are groups independently selectedrespectively from the group consisting of hydrogen, alkyl, substitutedor non-substituted aryl and substituted or non-substituted arylalkyl; Mis a monovalent alkali metal atom; in this alkyl, optional hydrogen maybe substituted with fluorine, and optional —CH₂— may be substituted with—O—, —CH═CH—, cycloalkylene or cycloalkenylene; and in alkylene in thisarylalkyl, optional hydrogen may be substituted with fluorine, andoptional —CH₂— may be substituted with —O— or —CH═CH—.[18] A production process for a silicon compound represented by Formula(5), characterized by reacting a compound represented by Formula (6)with a compound represented by Formula (4):

in Formula (6), R¹ is one group selected from the group consisting ofalkyl having a carbon number of 1 to 8, phenyl, non-substituted naphthyland phenylalkyl; M is a monovalent alkali metal atom; in the alkylhaving a carbon number of 1 to 8, optional hydrogen may be substitutedwith fluorine, and optional —CH₂— may be substituted with —O—, —CH═CH—,cycloalkylene or cycloalkenylene; optional hydrogen in the phenyl may besubstituted with halogen, methyl or methoxy; in the phenylalkyl,optional hydrogen on a benzene ring may be substituted with fluorine,alkyl having 1 to 4 carbon atoms, ethenyl or methoxy, and optional —CH₂—in alkylene may be substituted with —O—;R¹ in Formula (5) has the same meaning as that of R¹ in Formula (6);in Formula (4), X is halogen; R² is alkyl having 1 to 3 carbon atoms; ais an integer of 0 to 2; Z² is a single bond or alkylene having a carbonnumber of 1 to 8; in the alkylene having a carbon number of 1 to 8,optional —CH₂— may be substituted with —O—, —COO— or —OCO—; both of thebonding positions of halogenated sulfonyl and R² on a benzene ring areoptional positions; and the meanings of X, R², a, and Z² in Formula (5)and the bonding positions of halogenated sulfonyl and R² on a benzenering are the same as those in Formula (4).[19] A polymer obtained by polymerizing a vinyl monomer using thesilicon compound represented by Formula (1) as described in the item [1]as an initiator and a transition metal complex as a catalyst.[20] A polymer represented by Formula (7) obtained by polymerizing avinyl monomer using the silicon compound represented by Formula (1) asdescribed in the item [18] as an initiator and a transition metalcomplex as a catalyst:

the meanings of R¹, Z², R², a, and X in Formula (7) and the bondingpositions of halogenated sulfonyl and R² on a benzene ring are the sameas those in Formula (6) as described in the item [18], and P is a vinylpolymer.[21] The polymer as described in the item [19] or [20], wherein thevinyl monomer is at least one selected from the group consisting of a(meth)acrylic acid derivative and a styrene derivative.[22] The polymer as described in the item [19] or [20], wherein thevinyl monomer is at least one selected from the group consisting of the(meth)acrylic acid derivatives.[23] A polymerization process for a vinyl monomer characterized by usingthe silicon compound represented by Formula (1) as described in the item[1] as an initiator and using a transition metal complex as a catalyst.[24] A production process for the polymer represented by Formula (7) asdescribed in the item [20], characterized by polymerizing a vinylmonomer using the compound represented by Formula (5) as described inthe item [18] as an initiator and using a transition metal complex as acatalyst.

BEST MODE FOR CARRYING OUT THE INVENTION

In the following explanations, the compound represented by Formula (1)shall be described as the compound (1). The compound represented byFormula (2) shall be described as the compound (2). The compoundsrepresented by the other Formulas shall be described by the sameabbreviation.

In the present invention, both of alkyl and alkylene may be lineargroups or branched groups. For example, a group in which two —CH₂— inalkyl each are substituted with —O— and —CH═CH— is alkyloxyalkenyl oralkenyloxyalkyl, and any of alkyl, alkenylene, alkenyl and alkylene maybe a linear group or a branched group. Both of cycloalkyl andcycloalkenyl may be groups having a cross-linked cyclic structure or maynot be such groups. The term “optional” used in the present invention isused when it is shown that not only the position but also the number canoptionally be selected. Provided that when it is defined that optional—CH₂— may be substituted with —O—, it does not include a case whereplural continuous —CH₂— are substituted with —O—, and it does notinclude as well a case where —CH₂— bonded to a silicon atom issubstituted with —O—.

In Formula (1), seven R¹'s are groups independently selectedrespectively from the group consisting of hydrogen, alkyl, substitutedor non-substituted aryl and substituted or non-substituted arylalkyl.All R¹ is are preferably the same one group but may be constituted fromtwo or more different groups. The examples of a case where seven R¹'sare constituted from different groups are a case where they areconstituted from two or more alkyls, a case where they are constitutedfrom two or more aryls, a case where they are constituted from two ormore aralkyls, a case where they are constituted from hydrogen and atleast one aryl, a case where they are constituted from at least onealkyl and at least one aryl, a case where they are constituted from atleast one alkyl and at least one aralkyl and a case where they areconstituted from at least one aryl and at least one aralkyl. They may becombinations other than these cases. The compound (1) having at leasttwo different R¹ is can be obtained by using two or more raw materialswhen producing it. This raw material shall be described later.

When R¹ is alkyl, it has a carbon number of 1 to 45. The preferredcarbon number is 1 to 30. The more preferred carbon number is 1 to 8.Optional hydrogen thereof may be substituted with fluorine, and optional—CH₂— may be substituted with —O—, —CH═CH—, cycloalkylene orcycloalkenylene. The preferred examples of the alkyl are non-substitutedalkyl having a carbon number of 1 to 30, alkoxyalkyl having a carbonnumber of 2 to 29, a group in which one —CH₂— is substituted withcycloalkylene in alkyl having a carbon number of 1 to 8, alkenyl havinga carbon number of 2 to 20, alkenyloxyalkyl having a carbon number of 2to 20, alkyloxyalkenyl having a carbon number of 2 to 20, a group inwhich one —CH₂— is substituted with cycloalkenylene in alkyl having acarbon number of 1 to 8 and groups in which optional hydrogen(s) is/aresubstituted with fluorine in these groups. The preferred carbon numbersof cycloalkylene and cycloalkenylene are 3 to 8.

The examples of the non-substituted alkyl having a carbon number of 1 to30 are methyl, ethyl, propyl, 1-methylethyl, butyl, 2-methylpropyl,1,1-dimethylethyl, pentyl, hexyl, 1,1,2-trimethylpropyl, heptyl, octyl,2,4,4-trimethylpentyl, nonyl, decyl, undecyl, dodecyl, tetradecyl,hexadecyl, octadecyl, eicosyl, docosyl, triacontyl, and the like. Theexamples of the fluorinated alkyl having a carbon number of 1 to 30 are3,3,3-trifluoropropyl, 3,3,4,4,5,5,6,6,6-nonadecafluorohexyl,tridecafluoro-1,1,2,2-tetrahydrooctyl,heptadecafluoro-1,1,2,2-tetrahydrodecyl, perfluoro-1H,1H,2H,2H-dodecyl,perfluoro-1H,1H,2H,2H-tetradecyl, and the like. The examples of thealkoxyalkyl having a carbon number of 2 to 29 are 3-methoxypropyl,methoxyethoxyundecyl, 3-heptafluoroisopropoxypropyl, and the like. Theexamples of the group in which one —CH₂— is substituted withcycloalkylene in alkyl having a carbon number of 1 to 8 arecyclohexylmethyl, adamantaneethyl, cyclopentyl, cyclohexyl,2-bicycloheptyl, cyclooctyl, and the like. Cyclohexyl is an example inwhich —CH₂— in methyl is substituted with cyclohexylene.Cyclohexylmethyl is an example in which —CH₂— in ethyl is substitutedwith cyclohexylene.

The examples of the alkenyl having a carbon number of 2 to 20 areethenyl, 2-propenyl, 3-butenyl, 5-hexenyl, 7-octenyl, 10-undecenyl,21-docosenyl, and the like. The example of the alkenyloxyalkyl having acarbon number of 2 to 20 is allyloxyundecyl. The examples of the groupin which one —CH₂— is substituted with cycloalkenylene in alkyl having acarbon number of 1 to 8 are 2-(3-cyclohexenyl)ethyl,5-(bicycloheptenyl)ethyl, 2-cyclopentenyl, 3-cyclohexenyl,5-norbornene-2-yl, 4-cyclooctenyl, and the like.

The examples of a case where R¹ in Formula (1) is substituted ornon-substituted aryl are phenyl in which optional hydrogen may besubstituted with halogen or alkyl having a carbon number of 1 to 10 andnon-substituted naphthyl. The preferred examples of halogen are afluorine atom, a chlorine atom and bromine. In the alkyl having a carbonnumber of 1 to 10, optional hydrogen may be substituted with fluorine,and optional —CH₂— may be substituted with —O—, —CH═CH— or phenylene.That is, the preferred examples of the case where R¹ is substituted ornon-substituted aryl are non-substituted phenyl, non-substitutednaphthyl, alkylphenyl, alkyloxyphenyl, alkenylphenyl, phenyl having as asubstituent, a group in which optional —CH₂— in the alkyl having acarbon number of 1 to 10 is substituted with phenylene, groups in whichoptional hydrogen are substituted with halogen in these groups, and thelike.

The examples of the halogenated phenyl are pentafluorophenyl,4-chlorophenyl, 4-bromophenyl, and the like. The examples of thealkylphenyl are 4-methylphenyl, 4-ethylphenyl, 4-propylphenyl,4-butylphenyl, 4-pentylphenyl, 4-heptylphenyl, 4-octylphenyl,4-nonylphenyl, 4-decylphenyl, 2,4-dimethylphenyl, 2,4,6-trimethylphenyl,2,4,6-triethylphenyl, 4-(1-methylethyl)phenyl,4-(1,1-dimethylethyl)phenyl, 4-(2-ethylhexyl)phenyl,2,4,6-tris(1-methylethyl)phenyl, and the like. The examples of thealkyloxyphenyl are (4-methoxy)phenyl, (4-ethoxy)phenyl,(4-propoxy)phenyl, (4-butoxy)phenyl, (4-pentyloxy)phenyl,(4-heptyloxy)phenyl, (4-decyloxy)phenyl, (4-octadecyloxy)phenyl,4-(1-methylethoxy)phenyl, 4-(2-methylpropoxy)phenyl,4-(1,1-dimethylethoxy)phenyl, and the like. The examples of thealkenylphenyl are 4-ethenylphenyl, 4-(1-methylethenyl)phenyl,4-(3-butenyl)phenyl, and the like.

The examples of the phenyl having as a substituent, a group in whichoptional —CH₂— in the alkyl having a carbon number of 1 to 10 issubstituted with phenylene are 4-(2-phenylethenyl)phenyl,4-phenoxyphenyl, 3-(phenylmethyl)phenyl, biphenyl, terphenyl, and thelike. 4-(2-Phenylethenyl)phenyl is an example in which one —CH₂— inethyl of ethylphenyl is substituted with phenylene and in which theother —CH₂— is substituted with —CH═CH—.

The examples of the phenyl in which a part of hydrogens on a benzenering is substituted with halogen and in which the other hydrogens aresubstituted with alkyl, alkyloxy or alkenyl are 3-chloro-4-methylphenyl,2,5-dichloro-4-methylphenyl, 3,5-dichloro-4-methylphenyl,2,3,5-trichloro-4-methylphenyl, 2,3,6-trichloro-4-methylphenyl,3-bromo-4-methylphenyl, 2,5-dibromo-4-methylphenyl,3,5-dibromo-4-methylphenyl, 2,3-difluoro-4-methylphenyl,3-chloro-4-methoxyphenyl, 3-bromo-4-methoxyphenyl,3,5-dibromo-4-methoxyphenyl, 2,3-difluoro-4-methoxyphenyl,2,3-difluoro-4-ethoxyphenyl, 2,3-difluoro-4-propoxyphenyl,4-ethenyl-2,3,5,6-tetrafluorophenyl, and the like.

Next, the examples of a case where R¹ in Formula (1) is substituted ornon-substituted arylalkyl shall be given. In alkylene of the arylalkyl,optional hydrogen may be substituted with fluorine, and optional —CH₂—may be substituted with —O— or —CH═CH—. The preferred example of thearylalkyl is phenylalkyl. In this case, the preferred carbon number ofthe alkylene is 1 to 12, and the more preferred carbon number is 1 to 8.The examples of the non-substituted phenylalkyl are phenylmethyl,2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl,6-phenylhexyl, 11-phenylundecyl, 1-phenylethyl, 2-phenylpropyl,1-methyl-2-phenylethyl, 1-phenylpropyl, 3-phenylbutyl,1-methyl-3-phenylpropyl, 2-phenylbutyl, 2-methyl-2-phenylpropyl,1-phenylhexyl, and the like.

In the phenylalkyl, optional hydrogen on a benzene ring may besubstituted with halogen or alkyl having a carbon number of 1 to 12. Inthis alkyl having a carbon number of 1 to 12, optional hydrogen may besubstituted with fluorine, and optional —CH₂— may be substituted with—O—, —CH═CH—, cycloalkylene or phenylene. The examples of thephenylalkyl in which optional hydrogen on phenyl are substituted withfluorine are 4-fluorophenylmethyl, 2,3,4,5,6-pentafluorophenylmethyl,2-(2,3,4,5,6-pentafluorophenyl)ethyl,3-(2,3,4,5,6-pentafluorophenyl)propyl, 2-(2-fluorophenyl)propyl,2-(4-fluorophenyl)propyl, and the like.

The examples of the phenylalkyl in which hydrogens on a benzene ring aresubstituted with chlorine are 4-chlorophenylmethyl,2-chlorophenylmethyl, 2,6-dichlorophenylmethyl,2,4-dichlorophenylmethyl, 2,3,6-trichlorophenylmethyl,2,4,6-trichlorophenylmethyl, 2,4,5-trichlorophenylmethyl,2,3,4,6-tetrachlorophenylmethyl, 2,3,4,5,6-pentachlorophenylmethyl,2-(2-chlorophenyl)ethyl, 2-(4-chlorophenyl)ethyl,2-(2,4,5-chlorophenyl)ethyl, 2-(2,3,6-chlorophenyl)ethyl,3-(3-chlorophenyl)propyl, 3-(4-chlorophenyl)propyl,3-(2,4,5-trichlorophenyl)propyl, 3-(2,3,6-trichlorophenyl)propyl,4-(2-chlorophenyl)butyl, 4-(3-chlorophenyl)butyl,4-(4-chlorophenyl)butyl, 4-(2,3,6-trichlorophenyl)butyl,4-(2,4,5-trichlorophenyl)butyl, 1-(3-chlorophenyl)ethyl,1-(4-chlorophenyl)ethyl, 2-(4-chlorophenyl)propyl,2-(2-chlorophenyl)propyl, 1-(4-chlorophenyl)butyl, and the like.

The examples of the phenylalkyl in which hydrogens on phenyl aresubstituted with bromine are 2-bromophenylmethyl, 4-bromophenylmethyl,2,4-dibromophenylmethyl, 2,4,6-tribromophenylmethyl,2,3,4,5-tetrabromophenylmethyl, 2,3,4,5,6-pentabromophenylmethyl,2-(4-bromophenyl)ethyl, 3-(4-bromophenyl)propyl,3-(3-bromophenyl)propyl, 4-(4-bromophenyl)butyl, 1-(4-bromophenyl)ethyl,2-(2-bromophenyl)propyl, 2-(4-bromophenyl)propyl, and the like.

The examples of the phenylalkyl in which hydrogens on a benzene ring aresubstituted with alkyl having a carbon number of 1 to 12 are2-methylphenylmethyl, 3-methylphenylmethyl, 4-methylphenylmethyl,4-dodecylphenylmethyl, 3,5-dimethylphenylmethyl,2-(4-methylphenyl)ethyl, 2-(3-methylphenyl)ethyl,2-(2,5-dimethylphenyl)ethyl, 2-(4-ethylphenyl)ethyl,2-(3-ethylphenyl)ethyl, 1-(4-methylphenyl)ethyl,1-(3-methylphenyl)ethyl, 1-(2-methylphenyl)ethyl,2-(4-methylphenyl)propyl, 2-(2-methylphenyl)propyl,2-(4-ethylphenyl)propyl, 2-(2-ethylphenyl)propyl,2-(2,3-dimethylphenyl)propyl, 2-(2,5-dimethylphenyl)propyl,2-(3,5-dimethylphenyl)-propyl, 2-(2,4-dimethylphenyl)propyl,2-(3,4-dimethylphenyl)propyl, 2-(2,5-dimethylphenyl)butyl,(4-(1-methylethyl)phenyl)methyl, 2-(4-(1,1-dimethylethyl)phenyl)ethyl,2-(4-(1-methylethyl)phenyl)propyl, 2-(3-(1-methylethyl)phenyl)propyl,and the like.

The examples of the phenylalkyl in which hydrogens on a benzene ring aresubstituted with alkyl having a carbon number of 1 to 12 and in whichhydrogens in this alkyl are substituted with fluorine are3-(trifluoromethyl)phenylethyl, 2-(4-trifluoromethylphenyl)ethyl,2-(4-nonafluorobutylphenyl)ethyl, 2-(4-tridecafluorohexylphenyl)ethyl,2-(4-heptadecafluorooctylphenyl)ethyl, 1-(3-trifluoromethylphenyl)ethyl,1-(4-trifluoromethylphenyl)ethyl, 1-(4-nonafluorobutylphenyl)ethyl,1-(4-tridecafluorohexylphenyl)ethyl,1-(4-heptadecafluorooctylphenyl)ethyl,2-(4-nonafluorobutylphenyl)propyl,1-methyl-1-(4-nonafluorobutylphenyl)ethyl,2-(4-tridecafluorohexylphenyl)propyl,1-methyl-1-(4-tridecafluorohexylphenyl)ethyl,2-(4-heptadecafluorooctylphenyl)propyl,1-methyl-1-(4-heptadecafluorooctyl)phenyl)ethyl, and the like.

The examples of the phenylalkyl in which hydrogens on a benzene ring aresubstituted with alkyl having a carbon number of 1 to 12 and in which—CH₂—in this alkyl is substituted with —CH═CH— are2-(4-ethenylphenyl)ethyl, 1-(4-ethenylphenyl)ethyl,1-(2-(2-propenyl)phenyl)ethyl, and the like. The examples of thephenylalkyl in which hydrogens on a benzene ring are substituted withalkyl having a carbon number of 1 to 12 and in which —CH₂— in this alkylis substituted with —O— are 4-methoxyphenylmethyl,3-methoxyphenylmethyl, 4-ethoxyphenylmethyl, 2-(4-methoxyphenyl)ethyl,3-(4-methoxyphenyl)propyl, 3-(2-methoxyphenyl)propyl,3-(3,4-dimethoxyphenyl)propyl, 11-(4-methoxyphenyl)undecyl,1-(4-methoxyphenyl)ethyl, 2-(3-methoxymethyl)phenyl)ethyl,3-(2-nonadecafluorodecenyloxyphenyl)propyl, and the like.

The examples of the phenylalkyl in which hydrogens on a benzene ring aresubstituted with alkyl having a carbon number of 1 to 12 and in whichone of —CH₂— in this alkyl is substituted with cycloalkylene are, togive examples thereof including a case where another —CH₂— issubstituted with —O—, are cyclopentylphenylmethyl,cyclopentyloxyphenylmethyl, cyclohexylphenylmethyl,cyclohexylphenylethyl, cyclohexylphenylpropyl,cyclohexyloxyphenylmethyl, and the like. The examples of the phenylalkylin which hydrogens on a benzene ring are substituted with alkyl having acarbon number of 1 to 12 and in which one of —CH₂— in this alkyl issubstituted with phenylene are, to give examples thereof including acase where another —CH₂— is substituted with —O—, are2-(4-phenoxyphenyl)ethyl, 2-(4-phenoxyphenyl)propyl,2-(2-phenoxyphenyl)propyl, 4-biphenylylmethyl, 3-biphenylylethyl,4-biphenylylethyl, 4-biphenylylpropyl, 2-(2-biphenylyl)propyl,2-(4-biphenylyl)propyl, and the like.

The examples of the phenylalkyl in which at least two hydrogens on abenzene ring are substituted with different groups are3-(2,5-dimethoxy-3,4,6-trimethylphenyl)propyl,3-chloro-2-methylphenylmethyl, 4-chloro-2-methylphenylmethyl,5-chloro-2-methylphenylmethyl, 6-chloro-2-methylphenylmethyl,2-chloro-4-methylphenylmethyl, 3-chloro-4-methylphenylmethyl,2,3-dichloro-4-methyl-phenylmethyl, 2,5-dichloro-4-methylphenylmethyl,3,5-dichloro-4-methylphenylmethyl, 2,3,5-trichloro-4-methylphenylmethyl,2,3,5,6-tetrachloro-4-methylphenylmethyl,(2,3,4,6-tetrachloro-5-methylphenyl)methyl,2,3,4,5-tetrachloro-6-methylphenylmethyl,4-chloro-3,5-dimethylphenylmethyl, 2-chloro-3,5-dimethylphenylmethyl,2,4-dichloro-3,5-dimethylphenylmethyl,2,6-dichloro-3,5-dimethylphenylmethyl,2,4,6-trichloro-3,5-dimethylphenylmethyl, 3-bromo-2-methylphenylmethyl,4-bromo-2-methylphenylmethyl, 5-bromo-2-methylphenylmethyl,6-bromo-2-methylphenylmethyl, 3-bromo-4-methylphenylmethyl,2,3-dibromo-(4-methylphenylmethyl, 2,3,5-tribromo-4-methylphenylmethyl,2,3,5,6-tetrabromo-4-methylphenylmethyl,11-(3-chloro-4-methoxyphenyl)undecyl, and the like.

The most preferred examples of phenyl in the phenylalkyl arenon-substituted phenyl and phenyl having at least one of fluorine, alkylhaving a carbon number of 1 to 4, ethenyl and methoxy as a substituent.

The examples of the phenylalkyl in which —CH₂— in alkylene issubstituted with —O— or —CH═CH— are 2-phenoxyethyl, 3-phenoxypropyl,4-phenoxybutyl, 1-phenylethenyl, 2-phenylethenyl, 3-phenyl-2-propenyl,4-phenyl-4-pentenyl, 13-phenyl-12-tridecenyl, and the like. The examplesof the phenylalkyl in which hydrogen on a benzene ring is substitutedwith fluorine or methyl are 4-fluorophenylethenyl,2,3-difluorophenylethenyl, 2,3,4,5,6-pentafluorophenylethenyl,4-methylphenylethenyl, and the like.

The most preferred examples of R¹ are alkyl having a carbon number of 1to 8 (for example, ethyl, isobutyl and isooctyl), phenyl, halogenatedphenyl, phenyl having at least one methyl, methoxyphenyl, naphthyl,phenylmethyl, phenylethyl, phenylbutyl, 2-phenylpropyl,1-methyl-2-phenylethyl, pentafluoropropyl, 4-ethylphenylethyl,3-ethylphenylethyl, 4-(1,1-dimethylethyl)phenylethyl,4-ethenylphenylethyl, 1-(4-ethenylphenyl)ethyl, 4-methoxyphenylpropyl,phenoxyethyl and phenoxypropyl.

A¹ in Formula (1) is an organic group having a halogenated sulfonylgroup. An atom transfer radical polymerization method is known as apolymerization method using this halogenated sulfonyl group as aninitiating group for radical polymerization. In this method, a metalcomplex comprising the eighth, ninth, tenth or eleventh element in theperiodic table as a central metal atom is used as a catalyst. It isknown that the halogenated sulfonyl group has an excellentpolymerization initiating ability in this atom transfer radicalpolymerization. In addition thereto, it is well known as well that thispolymerization is living polymerization-like. That is, the compound (1)has an excellent polymerization initiating ability under the presence ofa transition metal complex and can continue to maintain a livingpolymerizability. The compound (1) can start polymerization of allradically polymerizable monomers.

A halogenated sulfonyl group has a strong electrophilicity, andtherefore various silsesquioxane derivatives can be synthesized byreacting the silicon compound of the present invention with variousnucleophilic reagents. For example, possible are conversion intosulfonic acid by hydrolysis under an acid condition, conversion intosulfonic acid by hydrolysis under an acid condition and then conversioninto sulfonic acid salt by treating with sodium hydroxide, conversioninto sulfonic acid esters by reacting with various alcohols under abasic condition and conversion into sulfonamide by treating with ammoniaor amine. It is possible to make use of the silicon compound of thepresent invention as a protective group because it has such reactivity,and it is possible as well to make use of a derivative of sulfonamide asa sulfa agent (for example, antibacterial agent). It is possible as wellto carry out conversion into a mercapto group by using various reducingagents (for example, aluminum lithium hydride). It can be derived intoaromatic sulfone by various aromatic Grignard reagents. That is, thecompound (1) can be used not only as a polymerization initiator but alsoas an intermediate useful for various organic syntheses.

The preferred exampled of A¹ is a group represented by Formula (2):

in Formula (2), X is halogen; R² is alkyl having 1 to 3 carbon atoms; ais an integer of 0 to 2; and Z¹ is a single bond or alkylene having acarbon number of 1 to 10. In the alkylene having 1 to 10 carbon atoms,optional —CH₂— may be substituted with —O—, —COO— or —OCO—. Both of thebonding positions of halogenated sulfonyl and R² on a benzene ring areoptional positions. Z¹ is preferably Z²—C₂H₄—. In this case, Z² is asingle bond or alkylene having a carbon number of 1 to 8, and at leastone —CH₂— which is not adjacent in this alkylene may be substituted with—O—, —COO— or —OCO—. The most preferred example of Z² is —C₂H₄—. Theexamples of halogen are Cl, Br andI. An Initiating Group for the Atom Transfer Radical polymerization ismost preferably Cl and Br. Preferred a is 0.

Next, a part of the specific examples of the silicon compound of thepresent invention shall be shown in Tables 2 and 3 using codes definedin Table 1. These examples are examples of the following Formula (8). Inthis formula, R¹ is ethyl, 2-methylpropyl, 2,4,4-trimethylpentyl,cyclopentyl or phenyl, and Z² is a single bond or —CH₂—.

TABLE 1 Code Chemical formula Et —C₂H₅ iBu —CH₂CH(CH₃)₂ iOc—CH₂CH(CH₃)CH₂C(CH₃)₃ TFPr —CH₂CH₂CF₃ CP

CH

Ph

— Single bond C1 —CH₂— C2 —C₂H₄— C3 —C₃H₆— C4 —C₄H₈— C5 —C₅H₁₀— CL —ClBR —Br

TABLE 2 No. R¹ Z² X Formula (8) 1 Et — CL (Et—)₇(CL—SO₂—Ph—C2—)Si₈O₁₂ 2iBu — CL (iBu—)₇(CL—SO₂—Ph—C2—)Si₈O₁₂ 3 iOc — CL(iOc—)₇(CL—SO₂—Ph—C2—)Si₈O₁₂ 4 TFPr — CL (TFPr—)₇(CL—SO₂—Ph—C2—)Si₈O₁₂ 5CP — CL (CP—)₇(CL—SO₂—Ph—C2—)Si₈O₁₂ 6 CH — CL(CH—)₇(CL—SO₂—Ph—C2—)Si₈O₁₂ 7 Ph — CL (Ph—)₇(CL—SO₂—Ph—C2—)Si₈O₁₂ 8 EtC1 CL (Et—)₇(CL—SO₂—Ph—C3—)Si₈O₁₂ 9 iBu C1 CL(iBu—)₇(CL—SO₂—Ph—C3—)Si₈O₁₂ 10 iOc C1 CL (iOc—)₇(CL—SO₂—Ph—C3—)Si₈O₁₂11 TFPr C1 CL (TFPr—)₇(CL—SO₂—Ph—C3—)Si₈O₁₂ 12 CP C1 CL(CP—)₇(CL—SO₂—Ph—C3—)Si₈O₁₂ 13 CH C1 CL (CH—)₇(CL—SO₂—Ph—C3—)Si₈O₁₂ 14Ph C1 CL (Ph—)₇(CL—SO₂—Ph—C3—)Si₈O₁₂ 15 Et C2 CL(Et—)₇(CL—SO₂—Ph—C4—)Si₈O₁₂ 16 iBu C2 CL (iBu—)₇(CL—SO₂—Ph—C4—)Si₈O₁₂ 17iOc C2 CL (iOc—)₇(CL—SO₂—Ph—C4—)Si₈O₁₂ 18 TFPr C2 CL(TFPr—)₇(CL—SO₂—Ph—C4—)Si₈O₁₂ 19 CP C2 CL (CP—)₇(CL—SO₂—Ph—C4—)Si₈O₁₂ 20CH C2 CL (CH—)₇(CL—SO₂—Ph—C4—)Si₈O₁₂ 21 Ph C2 CL(Ph—)₇(CL—SO₂—Ph—C4—)Si₈O₁₂ 22 Et C3 CL (Et—)₇(CL—SO₂—Ph—C5—)Si₈O₁₂ 23iBu C3 CL (iBu—)₇(CL—SO₂—Ph—C5—)Si₈O₁₂ 24 iOc C3 CL(iOc—)₇(CL—SO₂—Ph—C5—)Si₈O₁₂ 25 TFPr C3 CL (TFPr—)₇(CL—SO₂—Ph—C5—)Si₈O₁₂26 CP C3 CL (CP—)₇(CL—SO₂—Ph—C5—)Si₈O₁₂ 27 CH C3 CL(CH—)₇(CL—SO₂—Ph—C5—)Si₈O₁₂ 28 Ph C3 CL (Ph—)₇(CL—SO₂—Ph—C5—)Si₈O₁₂

TABLE 3 No. R¹ Z² X Formula (8) 1 Et — BR (Et—)₇(BR—SO₂—Ph—C2—)Si₈O₁₂ 2iBu — BR (iBu—)₇(BR—SO₂—Ph—C2—)Si₈O₁₂ 3 iOc — BR(iOc—)₇(BR—SO₂—Ph—C2—)Si₈O₁₂ 4 TFPr — BR (TFPr—)₇(BR—SO₂—Ph—C2—)Si₈O₁₂ 5CP — BR (CP—)₇(BR—SO₂—Ph—C2—)Si₈O₁₂ 6 CH — BR(CH—)₇(BR—SO₂—Ph—C2—)Si₈O₁₂ 7 Ph — BR (Ph—)₇(BR—SO₂—Ph—C2—)Si₈O₁₂ 8 EtC1 BR (Et—)₇(BR—SO₂—Ph—C3—)Si₈O₁₂ 9 iBu C1 BR(iBu—)₇(BR—SO₂—Ph—C3—)Si₈O₁₂ 10 iOc C1 BR (iOc—)₇(BR—SO₂—Ph—C3—)Si₈O₁₂11 TFPr C1 BR (TFPr—)₇(BR—SO₂—Ph—C3—)Si₈O₁₂ 12 CP C1 BR(CP—)₇(BR—SO₂—Ph—C3—)Si₈O₁₂ 13 CH C1 BR (CH—)₇(BR—SO₂—Ph—C3—)Si₈O₁₂ 14Ph C1 BR (Ph—)₇(BR—SO₂—Ph—C3—)Si₈O₁₂ 15 Et C2 BR(Et—)₇(BR—SO₂—Ph—C4—)Si₈O₁₂ 16 iBu C2 BR (iBu—)₇(BR—SO₂—Ph—C4—)Si₈O₁₂ 17iOc C2 BR (iOc—)₇(BR—SO₂—Ph—C4—)Si₈O₁₂ 18 TFPr C2 BR(TFPr—)₇(BR—SO₂—Ph—C4—)Si₈O₁₂ 19 CP C2 BR (CP—)₇(BR—SO₂—Ph—C4—)Si₈O₁₂ 20CH C2 BR (CH—)₇(BR—SO₂—Ph—C4—)Si₈O₁₂ 21 Ph C2 BR(Ph—)₇(BR—SO₂—Ph—C4—)Si₈O₁₂ 22 Et C3 BR (Et—)₇(BR—SO₂—Ph—C5—)Si₈O₁₂ 23iBu C3 BR (iBu—)₇(BR—SO₂—Ph—C5—)Si₈O₁₂ 24 iOc C3 BR(iOc—)₇(BR—SO₂—Ph—C5—)Si₈O₁₂ 25 TFPr C3 BR (TFPr—)₇(BR—SO₂—Ph—C5—)Si₈O₁₂26 CP C3 BR (CP—)₇(BR—SO₂—Ph—C5—)Si₈O₁₂ 27 CH C3 BR(CH—)₇(BR—SO₂—Ph—C5—)Si₈O₁₂ 28 Ph C3 BR (Ph—)₇(BR—SO₂—Ph—C5—)Si₈O₁₂

The examples shown in Table 2 and Table 3 are the preferred examples ofthe silicon compound of the present invention. The compound in which R¹in Formula (1) is non-substituted phenyl is most preferred.

Next, the production process for the silicon compound of the presentinvention shall be explained. The referred raw material of the presentinvention is a silicon compound having a silanol group represented byFormula (3):

R¹ in Formula (3) is the same as R¹ in Formula (1). Such compound can besynthesized by hydrolyzing chlorosilane and further ripening it. Forexample, Frank J. Feher et al. obtain a compound in which R¹ iscyclopentyl in Formula (3) by reacting cyclopentyltrichlorosilane in awater-acetone mixed solvent under a room temperature or refluxingtemperature and further ripening it for 2 weeks (Organometallics, 10,2526-(1991), Chemical European Journal, 3, No. 6, 900-(1997)).

The compound (1) can be produced by reacting the compound (3) withtrichlorosilane having a halogenated sulfonyl group making use of thereactivity of silanol (Si—OH).

Preferred trichlorosilane having a halogenated sulfonyl group is acompound (4). A compound (5) is obtained by reacting the compound (3)with the compound (4):

Considering to obtain the compound (3) as a commercially availableproduct, the preferred example of R¹ in Formula (3) is one groupselected from the group consisting of alkyl having a carbon number of 1to 8, phenyl, non-substituted naphthyl and phenylalkyl. Provided that inthe alkyl having a carbon number of 1 to 8, optional hydrogen may besubstituted with fluorine, and optional —CH₂— may be substituted with—O—, —CH═CH—, cycloalkylene or cycloalkenylene. Optional hydrogen in thephenyl may be substituted with halogen, methyl or methoxy. In thephenylalkyl, optional hydrogen on a benzene ring may be substituted withfluorine, alkyl having a carbon number of 1 to 4, ethenyl or methoxy,and optional —CH₂— in alkylene may be substituted with —O—. The othercodes in Formula (4) and Formula (5) have the same meanings as describedabove. The bonding positions of the halogenated sulfonyl group and R²are the same as described above.

In order to synthesize the compound (5) from the compound (3) and thecompound (4), capable of being adopted is a method called“Corner-capping reaction” (it is reaction making use of so-callednucleophilic substitution and described in, for example, Macromolecules,28, 8435-(1995)). The examples of the compound (4) are2-(4-chlorosulfonyl)ethyltrichlorosilane and3-(4-chlorosulfonyl)propyltrichlorosilane, but they shall not berestricted to them.

The selecting conditions of a solvent used for this nucleophilicsubstitution reaction is that it is not reacted with the compound (3)and the compound (4) and that it is sufficiently dehydrated. Theexamples of the solvent are tetrahydrofuran, toluene, dimethylforamide,and the like. The most preferred solvent is tetrahydrofuran which iswell dehydrated. The preferred use amount of the compound (4) is 1 to 5times in terms of an equivalent ratio based on an Si—OH group in thecase where it is reacted with the whole Si—OH (silanol) group of thecompound (3). In this reaction, hydrogen chloride is generated byreacting hydrogen of silanol with chlorine of chlorosilane, andtherefore this hydrogen chloride has to be removed from the reactionsystem. A method for removing hydrogen chloride shall not be restricted,and triethylamine is most preferably used. The preferred use amount oftriethylamine is 3 to 5 times in terms of an equivalent ratio based onan Si—OH group of the compound (3). The reaction temperature is atemperature which does not bring about side reactions at the same timeand which can allow quantitative nucleophilic substitution reaction toproceed. However, in charging the raw materials, it is most preferablycarried out under a low temperature condition, for example, in an icebath, and then it may be carried out under a a room temperature. Thereaction time shall not specifically be restricted as long as it issufficient time for allowing quantitative nucleophilic substitutionreaction to proceed, and the intended silicon compound can be obtainedusually in 13 hours.

Another preferred raw material used in the present invention is asilsesquioxane compound represented by Formula (6):

The compound (6) is obtained by reacting a silsesquioxane oligomerobtained by hydrolyzing a silane compound having a trifunctionalhydrolyzable group with monovalent alkali metal hydroxide in an organicsolvent. It is obtained as well by hydrolyzing and condensing a silanecompound having a trifunctional hydrolyzable group under the presence ofan organic solvent, water and alkali metal hydroxide. In the case of anymethods, the compound (6) can be produced at a high yield for short time(for example, refer to the specification of Application No.PCT/JP02/04776). The compound (6) shows a higher reactivity than that ofa silanol group in the compound (3). Accordingly, if this compound isused as the raw material, the derivative thereof can readily besynthesized at a high yield. Further, it has —ONa as a reactive group,and therefore if chlorosilanes are used for the synthetic reaction ofthe derivative, hydrogen chloride is not produced. Accordingly, thereaction operation can be facilitated, and it is possible to completelyreact it. That is, the compound (1) can readily be obtained from thecompound (6) and trichlorosilane having a halogenated sulfonyl group.

Also when using the compound (6), it is preferably reacted with thecompound (4) described above to prepare the compound (5). R¹ in Formula(6) is the same as R¹ in Formula (1), and the preferred examples thereofare the same as those in Formula (3). M in Formula (6) is a monovalentalkali metal atom. The preferred alkali metal is sodium and potassium.The most preferred example is sodium. Reaction in which the compound (6)is reacted with the compound (4) to prepare the compound (5) can becarried out as well in the same manner as in a case where the compound(3) is used. The preferred use amount of the compound (4) is 1 to 5times in terms of an equivalent ratio based on an Si—ONa group of thecompound (6). In this reaction, triethylamine does not have to be usedfor the purpose of removing hydrogen chloride. However, triethylaminemay be used as a catalytic role for allowing the reaction to quickly goon. When using triethylamine, it is added in an amount of 3 to 5 timesin terms of an equivalent ratio based on an Si—ONa group in the compound(6). A solvent, reaction temperature and reaction time used in thereaction are the same as in the reaction in which the compound (3) isused.

If a distillation method is applied in order to remove the unreacted rawmaterial compounds and solvent (hereinafter referred to as “impurities”in combination), the intended compound is likely to be decomposed bymaintaining for long time under a high temperature condition.Accordingly, a refining method by recrystallization operation ispreferably used in order to efficiently remove the impurities withoutdamaging a purity of the compound (5). This refining method is carriedout in the following manner. First, the compound (5) is dissolved in asolvent which dissolves both of the compound (5) and the impurities. Inthis case, the preferred concentration is, roughly speaking, 1 to 15% byweight. Next, the above solution is concentrated under a reducedpressure condition by means of a concentrating device, for example, arotary evaporator until crystal is started depositing. Then, thepressure is returned to an atmospheric pressure, and the reaction liquidis maintained at a room temperature or under a low temperaturecondition. Thereafter, the reaction liquid is subjected to filterfiltration or centrifugal separation, whereby a solid matted componentdeposited can be separated from the solvent containing impurities. It isa matter of course that the intended compound is contained as well inthe solvent containing the impurities, so that a recovering rate of thecompound (5) can be raised by repeatedly carrying out the operationdescribed above.

The selection conditions of the preferred solvent used forrecrystallization are no reaction with the compound (6), dissolving thecompound (6) and impurities at a stage before concentration, dissolvingonly the impurities and efficiently depositing the compound (6) inconcentration and having a relatively low boiling point. The examples ofthe preferred solvent satisfying such conditions are esters. Theparticularly preferred solvent is ethyl acetate. The frequency ofrepeating the recrystallization operation is advisably increased inorder to further raise the refining degree.

Next, an addition-polymerizable monomer for which the compound (1) canbe used as a polymerization initiator shall be explained. Thisaddition-polymerizable monomer is a monomer having at least oneaddition-polymerizable double bond. One of the examples of amonofunctional monomer having one addition-polymerizable double bond isa (meth)acrylic acid derivative. The specific examples thereof are(meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate,n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl(meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate,n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl(meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate,2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate,dodecyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate,benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxypropyl(meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl (meth)acrylate, stearyl (meth)acrylate,glycidyl (meth)acrylate, 3-ethyl-3-(meth)acryloyloxymethyloxetane,4-(meth)acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane,4-(meth)acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane,4-(meth)acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane,4-(meth)acryloyloxymethyl-2-cyclohexyl-1,3-dioxolane,2-(meth)acryloyloxyethyl-isocyanate, 2-aminoethyl (meth)acrylate,2-(2-bromopropanoylyloxy)ethyl (meth)acrylate,2-(2-bromoisobutyryloxy)ethyl (meth)acrylate,1-(meth)acryloxy-2-phenyl-2-(2,2,6,6-tetramethylpiperidinyloxy)ethane,(1-(4-((4-(meth)acryloxy)ethoxyethyl)phenylethoxy)piperidine,γ-(methacryloyloxypropyl)trimethoxysilane,3-(3,5,7,9,11,13,15-heptaethylpentacyclo-[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane-1-yl)propyl (meth)acrylate,3-(3,5,7,9,11,13,15-heptaisobutyl-pentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane-1-yl)propyl (meth)acrylate,3-(3,5,7,9,11,13,15-heptaisooctylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]-octasiloxane-1-yl)propyl(meth)acrylate,3-(3,5,7,9,11,13,15-heptacyclopentylpentacyclo-[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane-1-yl)propyl (meth)acrylate,3-(3,5,7,9,11,13,15-heptaphenylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]-octasiloxane-1-yl)propyl(meth)acrylate,3-[(3,5,7,9,11,13,15-heptaethylpentacyclo-[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane-1-yloxy)dimethylsilyl]propyl (meth)acrylate,3-[(3,5,7,9,11,13,15-heptaisobutylpentacyclo-[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane-1-yloxy)dimethylsilyl]propyl (meth)acrylate,3-[(3,5,7,9,11,13,15-heptaisooctylpentacyclo-[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane-1-yloxy)dimethylsilyl]propyl (meth)acrylate,3-[(3,5,7,9,11,13,15-heptacyclopentylpentacyclo-[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane-1-yloxy)dimethylsilyl]propyl (meth)acrylate,3-[(3,5,7,9,11,13,15-heptaphenylpentacyclo-[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane-1-yloxy)-dimethylsilyl]propyl (meth)acrylate, ethyleneoxide adducts of (meth)acrylic acid, trifluoromethylmethyl(meth)acrylate, 2-trifluoromethylethyl (meth)acrylate,2-perfluoroethylethyl (meth)acrylate,2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, 2-perfluoroethyl(meth)acrylate, trifluoromethyl (meth)acrylate, diperfluoromethylmethyl(meth)acrylate, 2-perfluoromethyl-2-perfluoroethylethyl (meth)acrylate,2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl(meth)acrylate, 2-perfluorohexadecylethyl (meth)acrylate, and the like.

Another example of the monofunctional monomer is a styrene base monomer.The specific examples thereof are styrene, vinyltoluene,α-methylstyrene, p-chlorostyrene, p-chloromethylstyrene,m-chloromethylstyrene, o-aminostyrene, p-styrenechlorosulfonic acid,styrenesulfonic acid and salts thereof, vinylphenylmethyldithiocarbamate, 2-(2-bromopropanonyloxy)styrene,2-(2-bromo-isobutyryloxy)styrene,1-(2-((4-ethenylphenyl)-methoxy)-1-phenylethoxy)-2,2,6,6-tetramethyl-piperidine,1-(4-vinylphenyl)-3,5,7,9,11,13,15-heptaethylpentacyclo-[9.5.1.1^(3,9).1^(5,15).1^(7,13)]-octasiloxane,1-(4-vinylphenyl)-3,5,7,9,11,13,15-heptaisobutylpentacyclo[9.5.1.1^(3,9).1^(5,1).1^(7,13)]-octasiloxane,1-(4-vinylphenyl)-3,5,7,9,11,13,15-heptaisooctylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]-octasiloxane,1-(4-vinylphenyl)-3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]-octasiloxane,1-(4-vinylphenyl)-3,5,7,9,11,13,15-heptaphenylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]-octasiloxane,3-(3,5,7,9,11,13,15-heptaethylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane-1-yl)ethylstyrene,3-(3,5,7,9,11,13,15-heptaisobutylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]-octasiloxane-1-yl)ethylstyrene,3-(3,5,7,9,11,13,15-heptaisooctylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]-octasiloxane-1-yl)ethylstyrene,3-(3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]-octasiloxane-1-yl)ethylstyrene,3-(3,5,7,9,11,13,15-heptaphenylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]-octasiloxane-1-yl)ethylstyrene,3-((3,5,7,9,11,13,15-heptaethylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane-1-yloxy)dimethylsilyl]ethylstyrene,3-((3,5,7,9,11,13,15-heptaisobutylpentacyclo-[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane-1-yloxy)dimethylsilyl)ethylstyrene,3-((3,5,7,9,11,13,15-heptaisooctylpentacyclo-[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane-1-yloxy)-dimethylsilyl)ethylstyrene,3-((3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]-octasiloxane-1-yloxy)dimethylsilyl)ethylstyrene,3-((3,5,7,9,11,13,15-heptaphenylpentacyclo-[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane-1-yloxy)dimethylsilyl]ethylstyrene,and the like.

The examples of the other monofunctional monomers arefluorine-containing vinyl monomers (perfluoroethylene,perfluoropropylene, vinylidene fluoride and the like),silicon-containing vinyl base monomers (vinyltrimethoxysilane,vinyltriethoxysilane and the like), maleic anhydride, maleic acid,monoalkyl esters and dialkyl esters of maleic acid, fumaric acid,monoalkyl esters and dialkyl esters of fumaric acid, maleimide basemonomers (maleimide, methylmaleimide, ethylmaleimide, propylmaleimide,butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide,stearylmaleimide, phenylmaleimide and cyclohexylmaleimide), nitrilegroup-containing monomers (acrylonitrile, methacrylonitrile and thelike), amide group-containing monomers (acrylamide, methacrylamide andthe like), vinyl ester base monomers (vinyl acetate, vinyl propionate,vinyl pivalate, vinyl benzoate, vinyl cinnamate and the like), olefins(ethylene, propylene and the like), conjugated diene base monomers(butadiene, isoprene and the like), halogenated vinyls (vinyl chlorideand the like), halogenated vinylidenes (vinylidene chloride and thelike), halogenated allyls (allyl chloride and the like), allyl alcohol,vinylpyrrolidone, vinylpyridine, N-vinylcarbazole, methyl vinyl ketone,vinylisocyanate, and the like. Further, given as well are macromonomerswhich have one polymerizable double bond in a molecule and in which aprincipal chain is derived from styrene, (meth)acrylic acid ester andsiloxane.

The examples of multifunctional monomers having twoaddition-polymerizable double bonds are 1,3-butanediol di(meth)acrylate,1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate,polyethylene glycol di(meth)acrylate, diethylene glycoldi(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycoldi(meth)acrylate, tripropylene glycol di(meth)acrylate, hydroxypivalicacid ester neopentyl glycol di(meth)acrylate, trimethylolpropanedi(meth)acrylate, bis[(meth)acryloyloxyethoxy] bisphenol A,bis[(meth)acryloyloxyethoxy] tetrabromobisphenol A,bis[(meth)acryloxypolyethoxy] bisphenol A,1,3-bis(hydroxyethyl)-5,5-dimethylhydantoin, 3-methylpentanedioldi(meth)acrylate, di(meth)acrylates of hydroxypivalic acid esterneopentyl glycol derivatives,bis[(meth)acryloyloxypropyl]-tetramethyldisiloxane, divinylbenzene, andthe like. Further, given as well are macromonomers which have twopolymerizable double bonds in a molecule and in which a principal chainis derived from styrene, (meth)acrylic acid ester and siloxane.

The examples of multifunctional monomers having three or moreaddition-polymerizable double bonds are trimethylolpropanetri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritoltetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate,tris(2-hydroxyethylisocyanate) tri(meth)acrylate, tris(diethyleneglycol)trimelate tri(meth)acrylate,3,7,14-tris[(((meth)acryloyloxypropyl)-dimethylsiloxy)]-1,3,5,7,9,11,14-heptaethyltricyclo-[7.3.3.1^(5,11)]heptasiloxane,3,7,14-tris[(((meth)acryloyloxypropyl)dimethylsiloxy)]-1,3,5,7,9,11,14-heptaisobutyltricyclo[7.3.3.1^(5,11)]-heptasiloxane,3,7,14-tris[(((meth)acryloyloxy-propyl)dimethylsiloxy)]-1,3,5,7,9,11,14-heptaisooctyltricyclo[7.3.3.1^(5,11)]heptasiloxane,3,7,14-tris[(((meth)acryloyloxypropyl)-dimethylsiloxy)]-1,3,5,7,9,11,14-heptacyclopentyl-tricyclo[7.3.3.1^(5,11)]heptasiloxane,3,7,14-tris[(((meth)acryloyloxypropyl)dimethylsiloxy)]-1,3,5,7,9,11,14-heptaphenyltricyclo[7.3.3.1^(5,11)]-heptasiloxane,octakis(3-(meth)acryloyloxypropyl-dimethylsiloxy)octasilsesquioxane,octakis(3-(meth)acryloyloxypropyl)octasilsesquioxane, and the like.Further, given as well are macromonomers which have two or morepolymerizable double bonds in a molecule and in which a principal chainis derived from styrene, (meth)acrylic acid ester and siloxane.

The monomers described above may be used alone or a plurality thereofmay be copolymerized. When copolymerized, they may berandom-copolymerized or block-copolymerized. The preferred monomers usedin the present invention are the (meth)acrylic acid derivatives and thestyrene derivatives. The more preferred monomers are the (meth)acrylicacid derivatives. The plural (meth)acrylic acid derivatives may becopolymerized, and the plural styrene derivatives may be copolymerized.At least one (meth)acrylic acid derivative may be copolymerized with atleast one styrene derivative.

Next, a method for subjecting a vinyl base monomer to atom transferradical polymerization using the compound (5) as an initiator and atransition metal complex as a catalyst shall be explained. The atomtransfer radical polymerization in the present invention is one ofliving radical polymerizations, and it is a method for radicallypolymerizing a vinyl monomer using an organic halide or a halogenatedsulfonyl compound as an initiator. This method is disclosed in J. Am.Chem. Soc., 1995, 117, 5614, Macromolecules, 1995, 28, 7901 and Science,1996, 272, 866.

The preferred example of a transition metal complex used as apolymerizing catalyst is a metal complex in which the 7th, 8th, 9th,10th or 11th group element in the periodic table is used as centermetal. More preferred catalyst is a complex of zero-valent cupper,monovalent cupper, divalent ruthenium, divalent iron or divalent nickel.Among them, the complex of cupper is preferred. The examples of amonovalent copper compound are cuprous chloride, cuprous bromide,cuprous iodide, cuprous cyanide, cuprous oxide and cuprous perchlorate.When using the copper compounds, 2,2′-bipyridyl or derivatives thereof,1,10-phenanthroline or derivatives thereof, pyridylmethaneimine(N-(n-propyl)-2-pyridylmethaneimine and the like), polyamine(tetramethylethylenediamine, pentamethyldiethylenetriamine,hexamethyltris(2-aminoethyl)amine and the like) or polycyclic alkaloidsuch as L-(−)-sparteine is added as a ligand in order to enhance thecatalyst activity. A tristriphenylphosphine complex (RuCl₂(PPh₃)₃) ofdivalent ruthenium chloride is also suited as the catalyst. When theruthenium compound is used as the catalyst, aluminum alkoxides are addedas an activating agent. Further, a bistriphenylphosphine complex(FeCl₂(PPh₃)₂) of divalent iron, a bistriphenylphosphine complex(NiCl₂(PPh₃)₂) of divalent nickel and a bistributylphosphine complex(NiBr₂(PBu₃)₂) of divalent nickel are also suited as the catalyst.

A solvent may be used for the polymerization reaction. The examples ofthe solvent used are hydrocarbon base solvents (benzene, toluene and thelike), ether base solvents (diethyl ether, tetrahydrofuran, diphenylether, anisole, dimethoxybenzene and the like), halogenated hydrocarbonbase solvents (methylene chloride, chloroform, chlorobenzene and thelike), ketone base solvents (acetone, methyl ethyl ketone, methylisobutyl ketone and the like), alcohol base solvents (methanol, ethanol,propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol and thelike), nitrile base solvents (acetonitrile, propionitrile, benzonitrileand the like), ester base solvents (ethyl acetate, butyl acetate and thelike), carbonate base solvents (ethylene carbonate, propylene carbonateand the like), amide base solvents (N,N-dimethylformamide,N,N-dimethylacetamide and the like), hydrochlorofluorocarbon basesolvents (HCFC-141b, HCFC-225), hydrofluorocarbon base solvents (HFCs),perfluorocarbon base solvents (perfluoropentane, perfluorohexane),alicyclic hydrofluorocarbon base solvents (fluorocyclopentane,fluorocyclobutane), oxygen-containing fluorine base solvents(fluoroether, fluoropolyether fluoroketone, fluoroalcohol), water, andthe like. They may be used alone or in combination of two or more kindsthereof. The polymerization can be carried out as well in an emulsionsystem or a system in which a supercritical fluid CO₂ is used as amedium. The solvent which can be used shall not be restricted to theseexamples.

The atom transfer radical polymerization can be carried out underreduced pressure, atmospheric pressure or applied pressure according tothe kind of the vinyl monomer and the kind of the solvent. An organicmetal complex used in combination or a radical produced is likely to bedeactivated when brought into contact with oxygen. In such case, thepolymerization rate is reduced, and a good living polymer is notobtained. Accordingly, it is important to carry out the polymerizationunder inert gas environment of nitrogen or argon. In this reaction,dissolved oxygen in the polymerization system has to be removed inadvance under reduced pressure. It is possible to shift to apolymerization step as it is under reduced pressure after finishing thestep of removing dissolved oxygen. The polymerization form of the atomtransfer radical polymerization shall not specifically be restricted,and a conventional process, for example, bulk polymerization, solutionpolymerization, suspension polymerization, emulsion polymerization orbulk-suspension polymerization can be adopted. The polymerizationtemperature falls in a range of 0 to 200° C., and the preferredpolymerization temperature falls in a range of a room temperature to150° C.

Next, controlling of the structure of the compound (7) shall beexplained. This compound is produced by the atom transfer radicalpolymerization method with the compound (5) being used as the initiatorand the transition metal complex being used as the catalyst:

P in this formula is a vinyl polymer, and the other marks and thebonding positions of the substituents each are the same as these marksand bonding positions in Formula (5).

Suitable selection of the kind of the vinyl base monomer used makes itpossible to control the structure of the compound (7) produced. Forexample, if the monomer is homopolymerized, silsesquioxane to which thehomopolymer is bonded is obtained. If the plural monomers are added atthe same time and polymerized, silsesquioxane to which the randomcopolymer is bonded is obtained. If used is a method in which themonomers are sequentially added, for example, a method in which thesecond monomer is added after finishing the polymerization of the firstmonomer to complete the polymerization, silsesquioxane to which a blockcopolymer is bonded is obtained. Repeating of this polymerization bystages using plural monomers makes it possible to obtain silsesquioxaneto which a multiblock copolymer is bonded. A cross-linked polymer havinga three-dimensional network structure can be prepared by allowing, ifnecessary, a multifunctional monomer to coexist.

Silsesquioxane to which a highly branched type polymer is bonded can beobtained by using in combination a compound (initiator-monomer) havingan initiator and a polymerizable functional group altogether, forexample, 2-2(bromopropionyloxy)ethyl (meth)acrylate,2-2(bromoisobutyryloxy)ethyl (meth)acrylate,2-2(bromopropionyloxy)styrene and 2-(2-bromoisobutyryloxy)styrene.Further, it is possible as well to positively introduce a siliconcompound by using in combination trialkoxysilane, polydimethylsiloxaneand silsesquioxane which have, for example, a (meth)acryl group and astyryl group as a polymerizable functional group. After copolymerizedwith a vinyl base monomer having an initiating group which does not takepart in atom transfer radical polymerization, for example,1-(2-((4-ethenylphenyl)methoxy)-1-phenylethoxy-2,2,6,6-tetramethylpyridine,1-(meth)acryloxy-2-phenyl-2-(2,2,6,6-tetramethylpiperidinyloxy)ethane,1-(4-((4-(meth)acryloxy)ethoxyethyl)phenylethoxy)piperidine orvinylphenylmethyldithiocarbamate, a vinyl base monomer is furtherpolymerized in the other polymerization mode (for example, nitroxylpolymerization and photo initiator-transfer agent-terminatorpolymerization) using the resulting polymer as an initiator, whereby agraft copolymer can be formed.

After copolymerized with a monomer having a glycidyl group, for example,glycidyl (meth)acrylate, a monomer having an oxetanyl group, forexample, 3-ethyl-3-(meth)acryloyloxymethyloxetane and a monomer havingdioxolane, for example,4-(meth)acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, an aliphaticsulfonium salt, an aromatic sulfonium salt or an aromatic iodonium saltas a thermally latent or optically latent cation polymerizationinitiator is added to the resulting polymer, whereby a cross-linkedpolymer having a three-dimensional network structure can be prepared bycation polymerization. The examples of the aliphatic sulfonium saltwhich is the thermally latent cation polymerization initiator are3-methyl-2-butenyltetramethylenesulfonium hexafluoroantimonate (AdekaOpton CP-77, commercial product manufactured by Asahi Denka Co., Ltd.)and 2-butenyltetramethylenesulfonium hexafluoroantimonate (Adeka OptonCP-66, commercial product manufactured by Asahi Denka Co., Ltd.), andthe examples of the aromatic sulfonium salt which is the thermally oroptically latent cation polymerization initiator are Sun Aid SI-15,SI-20, SI-25, SI-40, SI-45, SI-47, SI-60, SI-60L, SI-80, SI-80L, SI-100,SI-100L, SI-145, SI-150 and SI-160 (all are commercial productsmanufactured by Sanshin Chemical Industry Co., Ltd.), Adeka OptomerSP-172 and Adeka Optomer SP-152 (all are commercial productsmanufactured by Asahi Denka Co., Ltd.) anddiphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate. The exampleof the aromatic iodonium salt is (4-pentadecyloxyphenyl)-phenyliodoniumhexafluoroantimonate. When carrying out optically latent cationpolymerization, a photosensitizer, for example, Adeka Optomer SP-100(commercial product manufactured by Asahi Denka Co., Ltd.) may be usedin combination. Also, when obtaining a cross-linked polymer having athree-dimensional network structure by cation polymerization, amonofunctional or multifunctional glycidyl base cross-linking agent or amonofunctional or multifunctional oxetane base cross-linking agent maybe allowed to coexist.

Next, a refining method for the compound (7) shall be explained. Thiscompound is isolated and refined by efficiently removing the unreactedvinyl base monomer. Various methods are available, and a refining methodby reprecipitation operation is preferred. This refining method iscarried out in the following manner. First, a solvent which does notdissolve the compound (7) but dissolves the unreacted vinyl monomer, aso-called precipitant is added to a polymerization reaction liquidcontaining the compound (7) and the unreacted vinyl monomer toprecipitate only the compound (7). The preferred use amount of theprecipitant is 20 to 50 times based on the weight of the polymerizationreaction liquid containing the compound (7) and the unreacted vinylmonomer.

The preferred precipitant is a solvent which is compatible with thepolymerization solvent and which does not dissolve the compound (7) atall but dissolves only the unreacted vinyl monomer and which has arelatively low boiling point. The examples of the preferred precipitantare lower alcohols or aliphatic hydrocarbons. The particularly preferredprecipitant is hexane. A repeating frequency of the reprecipitationoperation is advisably increased in order to further raise a removingefficiency of the unreacted monomer. This method makes it possible todeposit only the compound (7) in the poor solvent, and the polymer canreadily be separated from the unreacted monomer by filtering operation.

The transition metal complex which is the polymerizing catalyst remainsin the compound (7) isolated by the method described above, andtherefore problems such as coloring of the polymer, influence on thephysical properties and environmental safety are brought about in acertain case. Accordingly, this catalyst residue has to be removed infinishing the polymerization reaction. The catalyst residue can beremoved by adsorbing treatment using activated carbon. The examples ofadsorbents other than activated carbon are ion exchange resins (acid,basic or chelate form) and inorganic adsorbents. The inorganic adsorbenthas a character of a solid acid, a solid base or neutrality. This is aparticle having a porous structure and therefore has a very highadsorbing ability. It is also one of the characteristics of theinorganic adsorbent that it can be used in a wide temperature rangeextending from a low temperature to a high temperature.

The examples of the inorganic adsorbent are silicon dioxide, magnesiumoxide, silica-alumina, aluminum silicate, activated alumina, clay baseadsorbents such as acid clay and activated clay, zeolite baseadsorbents, dawsonites compounds and hydrotalcites compounds. Zeoliteincludes natural products and synthetic products, and both can be used.Kinds such as a crystal form, an amorphous form, a noncrystal form, aglass form, a synthetic product and a natural product are available forsilicon dioxide, and silicon dioxide of a powder form can be used in thepresent invention regardless of the kind. The examples of naturalaluminum silicate are pumice, fly ash, kaoline, bentonite, activatedclay and diatomaceous earth. Synthetic aluminum silicate has a largespecific surface area and a high adsorbing ability. The hydrotalcitescompound is carbonate hydrate of aluminum-magnesium hydroxide.

The acid adsorbent and the basic adsorbent are preferably used incombination with activated carbon. The examples of the acid adsorbentare acid clay, activated clay, aluminum silicate, and the like. Theexamples of the basic adsorbent are activated alumina, the zeolite baseadsorbents, the hydrotalcites compounds each described above, and thelike. These adsorbents may be used alone or in a mixture of two or morekinds thereof. The compound (7) produced by the atom transfer radicalpolymerization can be refined by bringing into contact with activatedalumina. A commercial product available from Aldrich Co., Ltd. can beused as activated alumina. When adsorbing treatment is carried out byusing activated alumina in combination with the other adsorbent, theadsorbents can be mixed and brought into contact with the compound, butthey may be brought into contact at the separate steps respectively.When brought into contact with the adsorbent, the reaction liquid may beused as it is or may be diluted with a solvent. The diluent may beselected from usual solvents on the condition that only a poor solventfor the polymer is not used. A temperature for treating with theadsorbent shall not specifically be restricted. The treatment may becarried out usually at 0 to 200° C. The preferred temperature range is aroom temperature to 180° C. A use amount of the absorbent falls in arange of 0.1 to 500% by weight based on the weight of the compound (7).Considering the economical efficiency and the operability, the preferredrange is 0.5 to 10% by weight.

A method of a batch system in which stirring-mixing and solid-liquidseparation are carried out by batch operation can be used forsolid-liquid contact of the absorbent and the polymer liquid. Inaddition thereto, capable of being used is a method of a continuoussystem such as a fixed layer system in which the polymer liquid ispassed through a vessel charged with the adsorbent, a moving layersystem in which the liquid is passed through a moving layer of theadsorbent and a fluidized layer system in which the adsorbent isfluidized by a liquid to carry out adsorption. Further, mixing anddispersing operation carried out by stirring can be combined, ifnecessary, with operation for elevating the dispersing efficiency, suchas shaking of the vessel and use of a supersonic wave. After the polymerliquid is brought into contact with the absorbent, the absorbent isremoved by filtering, centrifugal separation and settling separation,and washing treatment is carried out if necessary to obtain the refinedpolymer liquid. Treatment by the absorbent is carried out for thepolymer (7) which is the final product, and it may be carried out for anintermediate product used for producing this polymer. For example, inthe respective polymerizing steps of the block copolymer obtained by theatom transfer radical polymerization, this polymer can be isolated andsubjected to adsorbing treatment. The polymer (7) subjected to treatmentby the adsorbent may be separated by depositing in a poor solvent ordistilling off volatile components such as the solvent under reducedpressure.

The analytical methods of a molecular weight and a molecular weightdistribution of the compound (7) produced shall be explained. Usually, amolecular weight of a vinyl polymer can be measured by gel permeationchromatography (GPC) using a calibration curve in which a linear polymersuch as polystyrene and methyl (meth)acrylate is used as a standardsample. Accordingly, the molecular weight and the molecular weightdistribution of the compound (7) produced can be analyzed by GPC.

The compound (7) has silsesquioxane at an end part thereof, andtherefore it can readily be decomposed under an acid condition or abasic condition. That is, an accuracy of molecular weight analysis of agrown polymer chain can further be enhanced by cutting off a vinyl basepolymer from silsesquioxane and then measuring the molecular weightthereof. Hydrofluoric acid is preferably used for decomposing thecompound (7) if decomposed under an acid condition, and potassiumhydroxide is preferably used if it is decomposed under a basiccondition. The compound (7) can be decomposed in either of a homogeneoussystem and an emulsion system. For example, the silsesquioxane part ofthe compound (7) can be decomposed in a mixed system of an organicsolvent (tetrahydrofuran, acetonitrile and the like) which can dissolvethe compound (7) and hydrofluoric acid. Further, the silsesquioxane partcan be decomposed as well in an emulsion system, for example, a mixedsystem of toluene and hydrofluoric acid, and in this case, a phasetransfer catalyst is preferably used in combination. When usingpotassium hydroxide, it can be decomposed as well in a mixed solvent oftetrahydrofuran, ethanol and water.

The vinyl polymer cut off by these methods is measured by GPC, whereby amolecular weight of the vinyl polymer contained in the compound (7) canbe determined. It is possible as well to determine a molecular weight ofthe compound (7) by using a universal calibration curve obtained fromthe viscosity and the GPC data. An absolute molecular weight of thecompound (7) can be determined as well by an end group determinationmethod, a membrane osmotic pressure method, an ultracentrifuge methodand a light scattering method.

A preferred molecular weight of the compound (7) falls in a range of 500to 1,000,000 in terms of a number average molecular weight calculated interms of polymethyl (meth)acrylate. The more preferred range is 1,000 to100,000. However, the upper limit value and the lower limit value inthis range do not necessarily have a specific meaning. The molecularweight distribution falls preferably in a range of 1.01 to 2.0 in termsof a dispersion degree (Mw/Mn).

The molecular weight of the compound (7) can be controlled by aproportion of the vinyl monomer to the compound (5) which is aninitiator. That is, a theoretical molecular weight of the compound (7)can be predicted from a mole ratio of the vinyl monomer/compound (5) anda consumption rate of the monomer using the following calculationequation:

Mn = (consumption  rate  (mole  %)  of  monomer/100) × MW_(M) × (mole  ratio  of  vinyl  base  monomer/compound  (5)) + MW_(I)In this calculation equation, Mn is a theoretical number averagemolecular weight; MW_(M) is a molecular weight of the vinyl basemonomer; and MW_(I) is a molecular weight of the compound (5).

When obtaining a polymer having the number average molecular weightrange described above, a mole ratio of the vinyl basemonomer/halogenated alkylphenyl group can be selected from a range ofabout 2/1 to about 40000/1, preferably about 10/1 to about 5000/1. Thisnumber average molecular weight can be controlled by changing thepolymerizing time. Any method of GPC, ¹H-NMR and gas chromatography canbe adopted as a method for determining a consumption rate (hereinafterreferred to as “conversion rate”) of the monomer.

The present invention shall more specifically be explained below withreference to examples, but the present invention shall not be restrictedto the examples.

Codes used in the examples mean the following.

-   Ph: phenyl-   CH: cyclohexyl-   CP: cyclopentyl-   Et: ethyl-   iBu: isobutyl-   iOc: isooctyl-   TFPr: trifluoropropyl-   TMS: trimethylsilyl-   Mn: number average molecular weight-   Mw: weight average molecular weight-   Tg: glass transition temperature-   Td: heat decomposition temperature

Analytical conditions in Examples 1 to 30 are shown below.

<GPC>

-   Apparatus: JASCO GULLIVER 1500 (intelligent differential    refractometer RI-1530), manufactured by JASCO Corp.-   Solvent: tetrahydrofuran-   Flow velocity: 1 ml/minute-   Column temperature: 40° C.-   Column used: TSKguardcolumn HXL-L (GUARDCOLUMN)+TSKgel G1000HxL    (exclusion limiting molecular weight (polystyrene):1,000)+TSKgel    G200H×L (exclusion limiting molecular weight (polystyrene):1,000)-   Standard sample for calibration curve: Polymer Standards (PL),    Polystyrene, manufactured by Polymer Laboratories Co., Ltd.

Analytical conditions in Examples 31 to 61 and Comparative Examples 1 to7 are shown below.

<GPC>

-   Apparatus: 8020 Series (detector: differential refractometer),    manufactured by Tosoh Corp.-   Solvent: tetrahydrofuran-   Flow velocity: 0.8 ml/minute-   Column temperature: 40° C.-   Column used: Shodex KF-LG (GUARDCOLUMN)+Shodex KF-804L (exclusion    limiting molecular weight (polystyrene):400000)×2 columns-   Standard sample for calibration curve: Polymer Standards (PL),    Poly(methyl methacrylate), manufactured by Polymer Laboratories Co.,    Ltd.    <Tg>-   Apparatus: differential scanning type calorimeter DSC7 (manufactured    by Perkin-Elmer Co., Ltd.)-   Heating rate: 10° C./minute-   Measuring temperature range: 10 to 180° C.-   <Td>-   Apparatus: thermogravimetric apparatus TGA7 (manufactured by    Perkin-Elmer Co., Ltd.)-   Heating rate: 20° C./minute-   Measuring temperature range: 50 to 800° C.

EXAMPLE 1

<Synthesis of Polyphenylsilsesquioxane (Compound A)>

A four neck separable flask having a content volume of 2 liter equippedwith a reflux condenser, a thermometer and a dropping funnel was chargedwith ice and water (640.7 g) and toluene (200 g), and the inside of theflask was cooled to 0° C. while stirring. Next, a mixed solution ofphenyltrichlorosilane (211.5 g) and toluene (130 g) dried on molecularsieves for a whole day and nigh was dropwise added thereto in one hourso that a temperature of the inside of the flask did not exceed 2° C.Then, after stirring at a room temperature for 30 minutes, the solutionwas washed with refined water, and toluene was distilled off underreduced pressure to obtain a solid compound A (120.7 g). The compound Ahad a weight average molecular weight of about 3100.

<Synthesis of Sodium-containing Phenylsilsesquioxane Compound (CompoundB)>

A 500 ml-four neck flask equipped with a reflux condenser and athermometer was charged with the compound A (12.9 g), tetrahydrofuran(250 ml) dried on molecular sieves for a whole day and night and sodiumhydroxide (4.0 g), and the flask was heated at 67° C. while stirring bymeans of a magnetic stirrer to maintain a reflux state. After about 4hours, the solution began to get cloudy by deposition of fine powder,and refluxing was continued for one hour as it was to finish thereaction. A solid matter deposited was washed with tetrahydrofuran andseparated from tetrahydrofuran by filtering, and then it was dried undervacuum to obtain a compound B (10.1 g).

EXAMPLE 2

<Introduction of Trimethylsilyl Group into Compound B (Compound C)>

A four neck flask of 200 ml equipped with a reflux condenser was chargedwith the compound B (2.0 g) obtained in Example 1, toluene (100 g),triethylamine (1.7 g) and trimethylchlorosilane (1.4 g), and the mixturewas stirred at a room temperature for 2 hours by means of a magneticstirrer. After finishing the reaction, it was washed with refined waterand dried under vacuum to obtain a compound C (2.1 g).

The compound C was subjected to structural analysis by means of ¹H-NMR,¹³C-NMR, ²⁹Si-NMR, mass spectrometry, X ray crystal structure analysisand IR analysis. It was confirmed from a ¹H-NMR chart and a ¹³C-NMRchart that a phenyl group and a trimethylsilyl group were present in anintegral ratio of 7:3. It was confirmed from ²⁹Si-NMR that three kindsof peaks of 11.547 ppm indicating a trimethylsilyl group, −77.574 ppm,−78.137 ppm and −78.424 ppm (all based on tetramethylsilane) having aphenyl group and indicating a T structure were present in a ratio of1:3:3. It was confirmed from the measuring results of a massspectrometric spectrum that the absolute molecular weight was consistentwith a theoretical molecular weight of a structural body represented byFormula (9). It was confirmed from the measuring results of crystalstructure analysis by X ray crystal structure analysis that the compoundwas the structural body represented by Formula (9). Confirmed from themeasuring results of an IR absorption spectrum were absorptions assignedrespectively to deformation vibration of Si—Ph in 1430 and 1590 cm⁻¹,harmonic vibration of a substituted benzene ring in 1960 to 1760 cm⁻¹,stretching vibration of Si—O—Si in 1200 to 950 cm⁻¹ and vibration ofSi—CH₃ in 1250 cm⁻¹. These results support that the compound (compoundC) replaced by a trimethylsilyl group has the structure represented byFormula (9), and this has made it apparent that the sodium-containingsilsesquioxane compound (compound B) obtained has a structurerepresented by Formula (10). The T structure means a structure in whichthree oxygen atoms are bonded to an Si atom.

EXAMPLE 3

<Synthesis of Sodium-containing Phenylsilsesquioxane Compound (CompoundB) Using Phenyltrimethoxysilane as Raw Material>

A four neck flask having a content volume of one liter equipped with areflux condenser, a thermometer and a dropping funnel was charged withphenyltrimethoxyosilane (99 g), sodium hydroxide (10 g) and 2-propanol(500 ml), and a stirrer bar was put thereinto. Deionized water 11 g wasdropwise added thereto from the dropping funnel in about 2 minutes whilestirring at a room temperature by means of a magnetic stirrer, and thenthe flask was heated on an oil bath up to a temperature at which2-propanol was refluxed. After refluxing was started, stirring wascontinued for 1.5 hour to complete the reaction. Then, the flask waspulled up from the oil bath and left standing still a night at a roomtemperature to completely deposit a solid matter produced. The solidmatter deposited was filtrated by means of a pressure filter equippedwith a membrane filter having a pore diameter of 0.1 μm. Then, the solidmatter thus obtained was washed once with 2-propanol and dried at 70° C.for 4 hours in a vacuum dryer to obtain a compound B (66 g) of a whitesolid.

EXAMPLE 4

<Introduction of Trimethylsilyl Group into Compound B Obtained UsingPhenyltrimethoxysilane as Raw Material (Compound C)>

A four neck flask having a content volume of 50 ml equipped with adropping funnel, a reflux condenser and a thermometer was charged with astirrer bar, the compound B (1.2 g) obtained in Example 3,tetrahydrofuran (12 g) and triethylamine (1.8 g), and the flask wassealed with dry nitrogen. Chlorotrimethylosilane (2.3 g) was dropwiseadded thereto from the dropping funnel at a room temperature in aboutone minute while stirring by means of a magnetic stirrer. Afterfinishing dropwise adding, stirring was continued at a room temperaturefor 3 hours to complete the reaction. Then, 10 g of purified water wasadded thereto to hydrolyze sodium chloride produced and unreactedchlorotrimethylsilane. The reaction mixture thus obtained wastransferred to a separating funnel and separated into an organic phaseand an aqueous phase, and the resulting organic phase was repeatedlywashed with deionized water until a washing liquid became neutral. Theorganic phase thus obtained was dried on anhydrous magnesium sulfate,filtered and concentrated under reduced pressure by means of a rotaryevaporator to obtain a compound C (1.2 g) of a white solid.

The compound C was subjected to structural analysis by means of ¹H-NMR,¹³C-NMR, ²⁹Si-NMR, mass spectrometry, X ray crystal structure analysisand IR analysis. It was confirmed from a ¹H-NMR chart and a ¹³C-NMRchart that a phenyl group and a trimethylsilyl group were present in anintegral ratio of 7:3. It was confirmed from ²⁹Si-NMR that three kindsof peaks of 11.547 ppm indicating a trimethylsilyl group, −77.574 ppm,−78.137 ppm and −78.424 ppm (all based on tetramethylsilane) having aphenyl group and indicating a T structure were present in a ratio of1:3:3. It was confirmed from the measuring results of a massspectrometric spectrum that the absolute molecular weight was consistentwith a theoretical molecular weight of the structure represented byFormula (9) described above. It was confirmed from the measuring resultsof crystal structure analysis by X ray crystal structure analysis thatthe compound was the structural body represented by Formula (9)described above. Confirmed from the measuring results of an IRabsorption spectrum were absorptions assigned respectively todeformation vibration of Si—Ph in 1430 and 1590 cm⁻¹, harmonic vibrationof a substituted benzene ring in 1960 to 1760 cm⁻¹, stretching vibrationof Si—O—Si in 1200 to 950 cm⁻¹ and vibration of Si—CH₃ in 1250 cm⁻¹.These results support that the compound (compound C) replaced by atrimethylsilyl group has the structure represented by Formula (9)described above, and this has made it apparent that thesodium-containing silsesquioxane compound (compound B) obtained has thestructure represented by Formula (10) described above. The T structuremeans a structure in which three oxygen atoms are bonded to an Si atom.

EXAMPLE 5

<Synthesis of Sodium-containing Cyclohexylsilsesquioxane Compound UsingCyclohexyltrimethoxysilane as Raw Material>

The same operation as in Example 3 is carried out, except thatcyclohexyltrimethoxysilane is substituted for phenyltrimethoxyosilane,whereby a sodium-containing cyclohexylsilsesquioxane compoundrepresented by Formula (11) can be obtained.

EXAMPLE 6

<Introduction of Trimethylsilyl Group into Compound (11)>

The same operation as in Example 4 is carried out, except that thecompound (11) is substituted for the compound (10), whereby atrimethylsilyl group-containing cyclohexylsilsesquioxane compoundrepresented by Formula (12) can be obtained. Further, it can beconfirmed by subjecting the compound (12) to structural analysis by thesame operation as in Example 4 that the compound (11) described above isproduced.

EXAMPLE 7

<Synthesis of Sodium-containing Cyclopentylsilsesquioxane Compound UsingCyclopentyltrimethoxysilane as Raw Material>

A four neck flask having a content volume of 200 ml equipped with areflux condenser, a thermometer and a dropping funnel was charged withcyclopentyltrimethoxyosilane (19.0 g), THF (100 ml), sodium hydroxide(1.7 g) and deionized water (2.3 g), and the flask was heated whilestirring by means of a magnetic stirrer. After refluxing was started at67° C., stirring was continued for 10 hours to finish the reaction.Then, the flask was pulled up from the oil bath and left standing stilla night at a room temperature to completely deposit a solid matterproduced. The solid matter deposited was filtrated and dried undervacuum to obtain a compound of a powder-like solid (4.2 g).

EXAMPLE 8

<Introduction of Trimethylsilyl Group>

A four neck flask having a content volume of 100 ml equipped with areflux condenser was charged with the compound (1.0 g) obtained inExample 7, THF (30 ml), triethylamine (0.5 g) and trimethylchlorosilane(0.7 g), and the mixture was stirred at a room temperature for 2 hourswhile stirring by means of a magnetic stirrer. After finishing thereaction, the same treatment as in confirming the structure in Example 4was carried out to obtain a compound of a powder-like solid (0.9 g).

The compound thus obtained was analyzed by means of ¹H-NMR, ²⁹Si-NMR andX ray crystal structure analysis. It was confirmed from ¹H-NMR that acyclopentyl group and a trimethylsilyl group were present in an integralratio of 7:3. Confirmed from ²⁹Si-NMR were 8.43 ppm indicating atrimethylsilyl group and three kinds of peaks of −66.37 ppm, −67.97 ppmand −67.99 ppm having a cyclopentyl group and indicating a T structure.A ratio of the sum of the peak intensities of −67.97 ppm and −67.99 ppmto a peak intensity of −66.37 ppm was 6:1. It was confirmed from theseresults and the crystal structure obtained by the X ray crystalstructure analysis that the compound of a powder-like solid matter whichwas the object of the analysis was a silicon compound represented byFormula (13). Accordingly, it was indicated that the compound obtainedin Example 7 had a structure represented by Formula (14).

EXAMPLE 9

<Synthesis of Sodium-containing Ethylsilsesquioxane Compound UsingEthyltrimethoxysilane as Raw Material>

The same operation as in Example 3 is carried out, except thatethyltrimethoxysilane is substituted for phenyltrimethoxyosilane,whereby a sodium-containing ethylsilsesquioxane compound represented byFormula (15) can be obtained.

EXAMPLE 10

<Introduction of Trimethylsilyl Group into Compound (15)>

The same operation as in Example 4 is carried out, except that thecompound (15) is substituted for the compound (10), whereby atrimethylsilyl group-containing ethylsilsesquioxane compound representedby Formula (16) can be obtained. Further, it can be confirmed bysubjecting the compound (16) to structural analysis by the sameoperation as in Example 4 that the compound (15) described above isproduced.

EXAMPLE 11

<Synthesis of Sodium-containing Isobutylsilsesquioxane Compound UsingIsobutyltrimethoxysilane as Raw Material>

A four neck flask having a content volume of 200 ml equipped with areflux condenser, a thermometer and a dropping funnel was charged withisobutyltrimethoxyosilane (18.7 g), THF (100 ml), sodium hydroxide (1.8g) and deionized water (2.4 g), and the flask was heated while stirringby means of a magnetic stirrer. After refluxing was started at 67° C.,stirring was continued for 10 hours to finish the reaction. The reactionliquid was concentrated under constant pressure until a solid matter wasdeposited, and then the resulting concentrate was left standing still anight at a room temperature to completely deposit the solid matter. Thiswas filtered and dried under vacuum to obtain a compound of apowder-like solid (5.1 g).

EXAMPLE 12

<Introduction of Trimethylsilyl Group>

A four neck flask having a content volume of 200 ml equipped with areflux condenser was charged with the compound of a powder-like solidmatter (1.0 g) obtained in Example 11, THF (20 ml), triethylamine (0.5g) and trimethylchlorosilane (0.8 g), and the mixture was stirred at aroom temperature for 2 hours while stirring by means of a magneticstirrer. After finishing the reaction, the same treatment as inconfirming the structure in Example 4 was carried out to obtain acompound of a powder-like solid matter (0.9 g).

The powder-like solid matter described above was subjected to structuralanalysis by means of ¹H-NMR and ²⁹Si-NMR. It was confirmed from a ¹H-NMRchart that an isobutyl group and a trimethylsilyl group were present inan integral ratio of 7:3. It was confirmed from ²⁹Si-NMR that threekinds of peaks of 8.72 ppm indicating a trimethylsilyl group, −67.38ppm, −68.01 ppm and −68.37 ppm having an isobutyl group and indicating aT structure were present in a ratio of 1:3:3. It was confirmed fromthese results that the compound of a powder-like solid matter which wasthe object of the analysis was a silicon compound represented by Formula(17). Accordingly, it was indicated that the compound obtained inExample 11 had a structure represented by Formula (18).

EXAMPLE 13

<Synthesis of Sodium-containing Isooctylsilsesquioxane>Compound UsingIsooctyltrimethoxysilane as Raw Material

The same operation as in Example 3 is carried out, except thatisooctyltrimethoxysilane is substituted for phenyltrimethoxyosilane,whereby a sodium-containing isooctylsilsesquioxane compound representedby Formula (19) can be obtained.

EXAMPLE 14

<Introduction of Trimethylsilyl Group into Compound (19)>

The same operation as in Example 4 is carried out, except that thecompound (19) is substituted for the compound (10), whereby atrimethylsilyl group-containing isooctylsilsesquioxane compoundrepresented by Formula (20) can be obtained. Further, it can beconfirmed by subjecting the compound (20) to structural analysis by thesame operation as in Example 4 that the compound (19) described above isproduced.

EXAMPLE 15

<Synthesis of Sodium-containing Trifluoropropylsilsesquioxane CompoundUsing Trifluoropropyltrimethoxysilane as Raw Material>

A four neck flask having a content volume of 1 liter equipped with areflux condenser, a thermometer and a dropping funnel was charged withtrifluoropropyltrimethoxyosilane (100 g), THF (500 ml), deionized water(10.5 g) and sodium hydroxide (7.9 g), and the flask was heated on anoil bath from a a room temperature up to a temperature at which THF wasrefluxed while stirring by means of a magnetic stirrer. After refluxingwas started, stirring was continued for 5 hours to complete thereaction. Thereafter, the flask was pulled up from the oil bath and leftstanding still a night at a a room temperature, and then the flask wasset again on the oil bath to heat and concentrate the reaction liquidunder constant pressure until a solid matter was deposited. The productdeposited was filtrated through a pressure filter equipped with amembrane filter having a pore diameter of 0.5 μm. Then, the solid matterthus obtained was washed once with THF and dried at 80 C for 3 hours ina vacuum dryer to obtain 74 g of a white power-like solid.

EXAMPLE 16

<Introduction of Trimethylsilyl Group>

A four neck flask having a content volume of 50 ml equipped with adropping funnel, a reflux condenser and a thermometer was charged withthe white power-like solid matter (1.0 g) obtained in Example 15, THF(10 g) and triethylamine (1.0 g), and the flask was sealed with drynitrogen. Chlorotrimethylsilane (3.3 g) was dropwise added thereto at aroom temperature in about one minute while stirring by means of amagnetic stirrer. After finishing dropwise adding, stirring wascontinued at a a room temperature for 3 hours to complete the reaction.Then, 10 g of purified water was added thereto to hydrolyze sodiumchloride produced and unreacted chlorotrimethylsilane. The reactionmixture thus obtained was transferred to a separating funnel andseparated into an organic phase and an aqueous phase, and the resultingorganic phase was repeatedly washed with deionized water until a washingliquid became neutral. The organic phase thus obtained was dried onanhydrous magnesium sulfate, filtered and concentrated under reducedpressure by means of a rotary evaporator to obtain a compound (0.9 g) ofa white solid.

The white powder-like solid obtained was subjected to structuralanalysis by means of GPC, ¹H-NMR, ²⁹Si-NMR and ¹³C-NMR. It was confirmedfrom a GPC chart that the white power-like solid matter showed amonodispersibility and had a weight average molecular weight of 1570 interms of polystyrene and a purity of 98% by weight. It was confirmedfrom a ¹H-NMR chart that a trifluoropropyl group and a trimethylsilylgroup were present in an integral ratio of 7:3. It was confirmed from a²⁹Si-NMR chart that three kinds of peaks having a trifluoropropyl groupand indicating a T structure were present in a ratio of 1:3:3 and thatone peak indicating a trimethylsilyl group was present in 12.11 ppm. Itwas confirmed from a ¹³C-NMR chart that peaks indicating atrifluoropropyl group were present in 131 to 123 ppm, 28 to 27 ppm and 6to 5 ppm and that a peak indicating a trimethylsilyl group was presentin 1.4 ppm. These values show that the white power-like solid matterwhich is an object for the structural analysis has a structure ofFormula (21). Accordingly, it is judged that the compound beforetrimethylsilylated has a structure of Formula (22).

EXAMPLE 17

<Synthesis of2-(4-chlorosulfonylphenyl)ethyl-heptaphenyloctasilsesquioxane Using theCompound (10) as Raw Material>

A 500 ml-four neck flask equipped with a dropping funnel, a refluxcondenser, a thermometer and a rotator was set in an ice bath, and 10 gof the compound (10) obtained in Example 1 and tetrahydrofuran (200 ml)were introduced into this four neck flask. The flask was sufficientlycooled by liquid nitrogen, and then added thereto was a2-(4-chlorosulfonylphenyl)ethyltrichlorosilane/methylene chloridesolution (50 wt %) (10.17 g, 1.5 equivalent based on the compound B).Thereafter, the flask was stirred again in the ice bath for further onehour, and then the reaction liquid was filtered. The solvent was removedfrom the filtrate by means of a rotary evaporator to obtain a viscousliquid. Ethyl acetate (100 ml) was added to this viscous liquid, andthen the liquid was concentrated by means of the rotary evaporator untilit turned cloudy and left standing still as it was for 4 hours under anatmospheric pressure. Thereafter, filtration was carried out by means ofa glass filter to obtain white crystal (1.16 g:yield 10%). This crystalwas dissolved in orthodichlorobenzene and measured by gaschromatography, and as a result thereof, the presence of impurities wasnot confirmed. A single peak was confirmed as well from the result ofGPC measurement, and the presence of the impurities was not confirmed.It was found from the results of IR, ¹H-NMR, ¹³C-NMR and ²⁹Si-NMR thatthe compound obtained had a structure represented by Formula (23).

IR: ν=1430 (Si-Ph), 1380, 1190 (—SO₂Cl), 1135 to 1090 (Si-Ph), 1090 to1020 (Si—O—Si) cm⁻¹

¹H NMR (400 MHz, CDCl₃, TMS standard: δ=0.0 ppm): δ7.79 to 7.30 (m, 39H,Si—[C₆H₅], —[C₆H₄]—SO₂Cl), 2.91 (t, 2H, —[CH₂]—C₆H₄—), 1.23 (t, 2H,Si—[CH₂]—)

¹³C NMR (100 MHz, CDCl₃, TMS standard: δ=0.0 ppm): 152.3, 142.0, 129.3,127.2 (—[C₆H₄]—SO₂Cl), 134.3, 131.1, 130.2, 128.1 (Si—[C₆H₅]), 29.0(—[CH₂]—C₆H₄—), 13.0 (Si—[CH₂]—)

²⁹Si NMR (CDCl₃, TMS standard: δ=0.0 ppm): −66.69 (—CH₂—[SiO_(1.5)]),−78.35, −78.41, −78.67 (C₆H₅— [SiO_(1.5)])

EXAMPLE 18

<Synthesis of2-(4-chlorosulfonylphenyl)ethyl-heptacyclohexyloctasilsesquioxane Usingthe Compound (11) as Raw Material>

The same operation as in Example 17 is carried out, except that thecompound (11) obtained in Example 5 is substituted for the compound(10), whereby a compound represented by Formula (24) can be obtained.

EXAMPLE 19

<Synthesis of2-(4-chlorosulfonylphenyl)ethyl-heptacyclopentyloctasilsesquioxane Usingthe Compound (14) as Raw Material>

The same operation as in Example 17 is carried out, except that thecompound (14) obtained in Example 7 is substituted for the compound(10), whereby a compound represented by Formula (25) can be obtained.

EXAMPLE 20

<Synthesis of2-(4-chlorosulfonylphenyl)ethyl-heptaethyloctasilsesquioxane Using theCompound (15) as Raw Material>

The same operation as in Example 17 is carried out, except that thecompound (15) obtained in Example 9 is substituted for the compound(10), whereby a compound represented by Formula (26) can be obtained.

EXAMPLE 21

<Synthesis of2-(4-chlorosulfonylphenyl)ethyl-heptaisobutyloctasilsesquioxane Usingthe Compound (18) as Raw Material>

The same operation as in Example 17 is carried out, except that thecompound (18) obtained in Example 11 is substituted for the compound(10), whereby a compound represented by Formula (27) can be obtained.

EXAMPLE 22

<Synthesis of2-(4-chlorosulfonylphenyl)ethyl-heptaisooctyloctasilsesquioxane Usingthe Compound (19) as Raw Material>

The same operation as in Example 17 is carried out, except that thecompound (19) obtained in Example 13 is substituted for the compound(10), whereby a compound represented by Formula (28) can be obtained.

EXAMPLE 23

<Synthesis of2-(4-chlorosulfonylphenyl)ethyl-heptatrifluoropropyloctasilsesquioxaneUsing the Compound (22) as Raw Material>

A 500 ml-four neck flask equipped with a dropping funnel, a refluxcondenser, a thermometer and a rotator was set in an ice bath, and 11.37g of the compound (22) obtained in Example 15, tetrahydrofuran (300 g)and triethylamine (1.5 g) were introduced into this four neck flask, andthe mixture was stirred. Added thereto was a2-(4-chlorosulfonylphenyl)ethyltrichlorosilane/methylene chloridesolution (50 wt %) (10.14 g, 1.5 equivalent based on the compound (22)),and the mixture was stirred for 3 hours, followed by filtering thereaction liquid. The solvent was removed from the filtrate by means of arotary evaporator to obtain a viscous liquid. Toluene was added to thisviscous liquid, and then the liquid was concentrated by means of therotary evaporator until it turned cloudy and left standing still as itwas for 4 hours under an atmospheric pressure. This operation wasrepeated three times, and then the deposit was dissolved again inmethylene chloride. Toluene was added thereto until the liquid turnedcloudy, and it was left standing still in a refrigerator of −34° C. Thisoperation was repeated twice, and then recrystallization was carried outfrom xylene to obtain colorless crystal (0.1 g: yield 0.77%) GPCmeasurement of this crystal was carried out to result in confirming asingle peak, and the presence of impurities was not confirmed. It wasfound from the results of ¹H-NMR, ¹³C-NMR and ²⁹Si-NMR that the compoundobtained had a structure represented by Formula (29).

¹H NMR (400 MHz, CDCl₃, TMS standard: δ=0.0 ppm): 7.98, 7.96, 7.45, 7.25(s, 4H, —[C₆H₄]—SO₂Cl), 2.83 (t, 2H, —[CH₂]—C₆H₄—), 2.15 (m, 14H,—[CH₂]-CF₃), 1.10 (t, 2H, Si—[CH₂]—CH₂—C₆H₄—), 0.95 (m, 14H,Si—[CH₂]—CH₂—CF₃),

¹³C NMR (100 MHz, CDCl₃, TMS standard: δ=0.0 ppm): 151.9, 142.5, 129.0,127.6 (—[C₆H₄]—SO₂Cl), 127.0 (—CH₂— [CF₃]), 28.9 (—[CH₂]—C₆H₄—), 27.9(—[CH₂]—CF₃), 13.0 (Si—[CH₂]—CH₂—C₆H₄—), 4.0 (Si—[CH₂]-CH₂—CF₃)

²⁹Si NMR (CDCl₃, TMS standard: δ=0.0 ppm): −67.54 (—CH₂—[SiO_(1.5)]),−67.60, −67.62, −67.73 (C₆H₅— [SiO_(1.5)])

EXAMPLE 24

<Synthesis of2-(4-chlorosulfonylphenyl)ethyl-heptaphenyloctasilsesquioxane Using theCompound (30) as Raw Material>

A compound represented by Formula (30) (10 g, trisilanolphenyl POSS,manufactured by Hybrid Plastics U.S Co., Ltd.), triethylamine (4.34 g,1.3 equivalent based on silanol) and tetrahydrofuran (250 ml) wereintroduced into a 500 ml-four neck flask equipped with a droppingfunnel, a reflux condenser, a thermometer and a rotator in an ice bath.Added thereto was a2-(4-chlorosulfonylphenyl)ethyl-trichlorosilane/methylene chloridesolution (50 wt %) (10.89 g, 1.5 equivalent based on the compound (30)),and the mixture was stirred at a room temperature for further one hour,followed by filtering the reaction liquid. The solvent was distilled offby means of a rotary evaporator to obtain a white viscous liquid. Ethylacetate (100 ml) was added to the viscous liquid obtained, and then theliquid was concentrated by means of the rotary evaporator until itturned cloudy and left standing still as it was for 4 hours under anatmospheric pressure. Thereafter, filtration wad carried out by means ofa glass filter (G3 grade) to obtain 1.28 g of colorless crystal (yield10%). The compound obtained was dissolved (30.2 wt %) inorthodichlorobenzene and measured by gas chromatography, and as a resultthereof, the presence of impurities was not confirmed. GPC measurementwas carried out to result in confirming a single peak, and the presenceof impurities was not confirmed. It was found from the results of IR,¹H-NMR, ¹³C-NMR and ²⁹Si-NMR that the compound had a structurerepresented by Formula (23) shown in Example 17.

IR: ν=1430 (Si-Ph), 1380, 1190 (—SO₂ Cl), 1135 to 1090 (Si-Ph), 1090 to1020 (Si—O—Si) cm⁻¹

¹H NMR (400 MHz, CDCl₃, TMS standard: δ=0.0 ppm): δ7.79 to 7.30 (m, 39H,Si—[C₆H₅], —[C₆H₄]—SO₂Cl), 2.91 (t, 2H, —[CH₂]—C₆H₄—), 1.23 (t, 2H,Si—[CH₂]—)

¹³C NMR (100 MHz, CDCl₃, TMS TMS standard: δ=0.0 ppm): 152.3, 142.0,129.3, 127.2 (—[C₆H₄]—SO₂Cl), 134.3, 131.1, 130.2, 128.1 (Si—[C₆H₅]),29.0 (—[CH₂]—C₆H₄—), 13.0 (Si—[CH₂]—)

²⁹Si NMR (CDCl₃, TMS standard: δ=0.0 ppm): −66.69 (—CH₂—[SiO_(1.5)]),−78.35, −78.41, −78.67 (C₆H₅— [SiO_(1.5)])

EXAMPLE 25

<Synthesis of2-(4-chlorosulfonylphenyl)ethyl-heptacyclohexyloctasilsesquioxane Usingthe Compound (31) as Raw Material>

The same operation as in Example 24 is carried out, except that acompound represented by Formula (31) (trisilanolcyclohexyl POSS,manufactured by Hybrid Plastics U.S Co., Ltd.) is substituted for thecompound (30), whereby the compound (24) described in Example 18 can beobtained.

EXAMPLE 26

<Synthesis of2-(4-chlorosulfonylphenyl)ethyl-heptacyclopentyloctasilsesquioxane Usingthe Compound (32) as Raw Material>

The same operation as in Example 24 is carried out, except that acompound represented by Formula (32) (trisilanolcyclopentyl POSS,manufactured by Hybrid Plastics U.S Co., Ltd.) is substituted for thecompound (30), whereby the compound (25) described in Example 19 can beobtained.

EXAMPLE 27

<Synthesis of2-(4-chlorosulfonylphenyl)ethyl-heptaethyloctasilsesquioxane Using theCompound (33) as Raw Material>

The same operation as in Example 24 is carried out, except that acompound represented by Formula (33) (trisilanolethyl POSS, manufacturedby Hybrid Plastics U.S Co., Ltd.) is substituted for the compound (30),whereby the compound (26) described in Example 20 can be obtained.

EXAMPLE 28

<Synthesis of2-(4-chlorosulfonylphenyl)ethyl-heptaisobutyloctasilsesquioxane Usingthe Compound (34) as Raw Material>

The same operation as in Example 24 is carried out, except that acompound represented by Formula (34) (trisilanolisobutyl POSS,manufactured by Hybrid Plastics U.S Co., Ltd.) is substituted for thecompound (30), whereby the compound (27) described in Example 21 can beobtained.

EXAMPLE 29

<Synthesis of2-(4-chlorosulfonylphenyl)ethyl-heptaisooctyloctasilsesquioxane Usingthe Compound (35) as Raw Material>

The same operation as in Example 24 is carried out, except that acompound represented by Formula (35) (trisilanolisooctyl POSS,manufactured by Hybrid Plastics U.S Co., Ltd.) is substituted for thecompound (30), whereby the compound (28) described in Example 22 can beobtained.

EXAMPLE 30

A 300 ml-four neck flask equipped with a dropping funnel, a refluxcondenser, a thermometer and a rotator was set in an ice bath. Thecompound (22) 5 g obtained in Example 15 was added to this four neckflask and dissolved in butyl acetate (50 g), and then acetic acid (0.5g) was dropwise added thereto. The flask was stirred for one hour as itwas put in the ice bath. After returned to a room temperature, thereaction liquid was washed (three times) with deionized water (100 ml).The solvent was distilled off by means of a rotary evaporator and dried(50° C., one hour) as it was under reduced pressure to obtain a viscousliquid (4.3 g). GPC measurement of the compound obtained was carried outto result in showing a single peak, and the presence of impurities wasnot confirmed. Further, analysis using IR was carried out to result inconfirming absorption (in the vicinity of 3400 cm⁻¹) indicating thepresence of a silanol group which was not observed in the compound (22).Accordingly, it was indicated that the compound obtained had a structurerepresented by Formula (36).

Chlorosulfonylphenylethyltrichlorosilane is reacted with the compound(36) described above which is a starting raw material under the presenceof triethylamine according to the method described in Examples 24 to 29described above, whereby the compound (29) can be derived.

EXAMPLE 31 <Preparation of Solution for Polymerization>

A compound (23)/methyl methacrylate/L-(−)-sparteine/anisole solution andcuprous bromide each were separately introduced into a feed forked heatresistant glass-made ampoule in a draft which was cut off from a UV ray.Then, freezing vacuum deaeration (pressure: 1.0 Pa) was carried outthree times by means of a vacuum device equipped with an oil-sealedrotary pump while taking care so that both were not mixed. The compound(23)/methyl methacrylate/L-(−)-sparteine/anisole solution was mixed withcuprous bromide in the feed forked heat resistant glass-made ampoulewhile maintaining a vacuum state, and then the ampoule was quicklysealed by means of a hand burner. In this solution for polymerization, aproportion of the compound (23), methyl methacrylate, cuprous bromideand L-(−)-sparteine was set in this order to 1:500:2:4 in terms of amole ratio, and a use amount of anisole was set to such an mount that aconcentration of methyl methacrylate was 50 wt %.

<Polymerization>

The sealed heat resistant glass-made ampoule was set in a constanttemperature shaking bath, and polymerization was carried out to obtain abrown viscous solution of a polymer (1a). In this case, thepolymerization temperature was 70° C., and the polymerization time was0.5 hour. Thereafter, the solution of the polymer (1a) was sampled anddiluted with tetrahydrofuran, and then it was subjected to GPCmeasurement. A monomer conversion rate in this polymerization reactionsystem was analyzed based on a peak area obtained from a GPC measuredvalue of a poly(methyl methacrylate) solution having a-knownconcentration. The analytical results of the monomer conversion rate andthe molecular weight and the molecular weight distribution of thepolymer (1a) are shown in Table 4.

EXAMPLE 32

Polymerization was carried out in the same manner as in Example 31 toobtain a brown viscous solution of a polymer (1b), except that thepolymerization time was changed to one hour. The monomer conversion rateand a molecular weight and a molecular weight distribution of thepolymer (1b) were determined in the same manner as in Example 31, andthe results thereof are shown Table 4.

EXAMPLE 33

Polymerization was carried out in the same manner as in Example 31 toobtain a brown viscous solution of a polymer (1c), except that thepolymerization time was changed to 2 hours. The monomer conversion rateand a molecular weight and a molecular weight distribution of thepolymer (1c) were determined in the same manner as in Example 31, andthe results thereof are shown Table 4.

EXAMPLE 34

Polymerization was carried out in the same manner as in Example 31 toobtain a brown viscous solution of a polymer (1d), except that thepolymerization time was changed to 3 hours. The monomer-conversion rateand a molecular weight and a molecular weight distribution of thepolymer (1d) were determined in the same manner as in Example 31, andthe results thereof are shown Table 4.

EXAMPLE 35

Polymerization was carried out in the same manner as in Example 31 toobtain a brown viscous solution of a polymer (1e), except that thepolymerization time was changed to 4 hours. The monomer conversion rateand a molecular weight and a molecular weight distribution of thepolymer (1e) were determined in the same manner as in Example 31, andthe results thereof are shown Table 4.

EXAMPLE 36

Polymerization was carried out in the same manner as in Example 31 toobtain a brown viscous solution of a polymer (1f), except that thepolymerization time was changed to 14 hours. The monomer conversion rateand a molecular weight and a molecular weight distribution of thepolymer (1f) were determined in the same manner as in Example 31, andthe results thereof are shown Table 4.

EXAMPLE 37

<Preparation of Solution for Polymerization>

In this example, a proportion of the compound (23), methyl methacrylate,cuprous bromide and L-(−)-sparteine in the solution for polymerizationwas set in this order to 1:500:1:2 in terms of a mole ratio. Anisole wasused so that a concentration of methyl methacrylate in the solution forpolymerization was 50 wt %.

A compound (23)/methyl methacrylate/L-(−)-sparteine/anisole solution andcuprous bromide each were separately introduced into a feed forked heatresistant glass-made ampoule in a draft which was cut off from a UV ray.Then, freezing vacuum deaeration (pressure: 1.0 Pa) was carried out bymeans of the vacuum device equipped with an oil-sealed rotary pump whiletaking care so that both were not mixed. The frozen solution was moltenat a room temperature, and dry argon gas was filled therein. Theoperation of carrying out freezing vacuum deaeration and filling ofargon gas was repeated three times in total, and then the compound(23)/methyl methacrylate/L-(−)-sparteine/anisole solution was mixed withcuprous bromide in the feed forked heat resistant glass-made ampoulewhile maintaining a state of filling argon gas, followed by quicklysealing the ampoule by means of a hand burner.

<Polymerization>

The sealed heat resistant glass-made ampoule was set in a constanttemperature shaking bath, and polymerization was carried out to obtain abrown viscous solution of a polymer (2a). In this case, thepolymerization temperature was 70° C., and the polymerization time wasone hour. Thereafter, the solution of the polymer (2a) was sampled anddiluted with tetrahydrofuran, and then it was subjected to GPCmeasurement. A monomer conversion rate in this polymerization reactionsystem was determined from the relation of a proton ratio ofsubstituents in the respective monomer and polymer by diluting thesolution of the polymer (2a) with deuterated chloroform and thensubjecting the solution to ¹H-NMR. The results obtained by analyzing themonomer conversion rate and a molecular weight and a molecular weightdistribution of the polymer (2a) are shown in Table 4.

EXAMPLE 38

Polymerization was carried out in the same manner as in Example 37 toobtain a brown viscous solution of a polymer (2b), except that thepolymerization time was changed to 2 hours. The monomer conversion rateand a molecular weight and a molecular weight distribution of thepolymer (2b) were determined in the same manner as in Example 37, andthe results thereof are shown Table 4.

TABLE 4 Conversion Number average Dispersion Example Polymer ratemolecular weight degree No. No. (mole-%) (Mn) (Mw/Mn) 31 1a 6.51 3,0001.11 32 1b 8.42 4,300 1.11 33 1c 16.7 9,400 1.10 34 1d 18.9 13,500 1.0935 1e 34.3 20,600 1.11 36 1f 67.3 39,600 1.13 37 2a 4.4 3,800 1.15 38 2b8.2 4,200 1.12

EXAMPLE 39

<Preparation of Solution for Polymerization>

In this example, a proportion of the compound (23), methyl methacrylate,cuprous bromide and L-(−)-sparteine in the solution for polymerizationwas set in this order to 1:300:1:2 in terms of a mole ratio. Anisole wasused so that a concentration of methyl methacrylate in the solution forpolymerization was 50 wt %.

A compound (23)/methyl methacrylate/L-(−)-sparteine/anisole solution andcuprous bromide each were separately introduced into a feed forked heatresistant glass-made ampoule in a draft which was cut off from a UV ray.Then, freezing vacuum deaeration (pressure: 1.0 Pa) was carried outthree times by means of the vacuum device equipped with an oil-sealedrotary pump while taking care so that both were not mixed. The compound(23)/methyl methacrylate/L-(−)-sparteine/anisole solution was mixed withcuprous bromide in the feed forked heat resistant glass-made ampoulewhile maintaining a state of vacuum, and then the ampoule was quicklysealed by means of a hand burner.

<Polymerization>

The sealed heat resistant glass-made ampoule was set in a constanttemperature shaking bath, and polymerization was carried out to obtain abrown viscous solution of a polymer (3a). In this case, thepolymerization temperature was 70° C., and the polymerization time was 2hours. The monomer conversion rate and a molecular weight and amolecular weight distribution of the polymer (3a) were determined in thesame manner as in Example 31, and the results thereof are shown in Table5.

EXAMPLE 40

Polymerization was carried out in the same manner as in Example 39 toobtain a brown viscous solution of a polymer (3b), except that thepolymerization time was changed to 4.2 hours. The monomer conversionrate and a molecular weight and a molecular weight distribution of thepolymer (3b) were determined in the same manner as in Example 31, andthe results thereof are shown Table 5.

EXAMPLE 41

Polymerization was carried out in the same manner as in Example 39 toobtain a brown viscous solution of a polymer (3c), except that thepolymerization time was changed to 6.2 hours. The monomer conversionrate and a molecular weight and a molecular weight distribution of thepolymer (3c) were determined in the same manner as in Example 31, andthe results thereof are shown Table 5.

EXAMPLE 42

Polymerization was carried out in the same manner as in Example 39 toobtain a brown viscous solution of a polymer (3d), except that thepolymerization time was changed to 9 hours. The monomer conversion rateand a molecular weight and a molecular weight distribution of thepolymer (3d) were determined in the same manner as in Example 31, andthe results thereof are shown Table 5.

EXAMPLE 43

Polymerization was carried out in the same manner as in Example 39 toobtain a brown viscous solution of a polymer (3e), except that thepolymerization time was changed to 12 hours. The monomer conversion rateand a molecular weight and a molecular weight distribution of thepolymer (3e) were determined in the same manner as in Example 31, andthe results thereof are shown Table 5.

EXAMPLE 44

Polymerization was carried out in the same manner as in Example 39 toobtain a brown viscous solution of a polymer (3f), except that thepolymerization time was changed to 20 hours. The monomer conversion rateand a molecular weight and a molecular weight distribution of thepolymer (3f) were determined in the same manner as in Example 31, andthe results thereof are shown Table 5.

EXAMPLE 45

Polymerization was carried out in the same manner as in Example 39 toobtain a brown viscous solution of a polymer (3g), except that thepolymerization time was changed to 6 hours. The monomer conversion rateand a molecular weight and a molecular weight distribution of thepolymer (3g) were determined in the same manner as in Example 31, andthe results thereof are shown Table 5.

EXAMPLE 46

Polymerization was carried out in the same manner as in Example 39 toobtain a brown viscous solution of a polymer (3h), except that thepolymerization time was changed to 8.5 hours. The monomer conversionrate and a molecular weight and a molecular weight distribution of thepolymer (3h) were determined in the same manner as in Example 31, andthe results thereof are shown Table 5.

EXAMPLE 47

Polymerization was carried out in the same manner as in Example 39 toobtain a brown viscous solution of a polymer (3i), except that thepolymerization time was changed to 11 hours. The monomer conversion rateand a molecular weight and a molecular weight distribution of thepolymer (3i) were determined in the same manner as in Example 31, andthe results thereof are shown Table 5.

EXAMPLE 48

<Preparation of Solution for Polymerization>

In this example, a proportion of the compound (23), methyl methacrylate,cuprous bromide and L-(−)-sparteine in the solution for polymerizationwas set in this order to 1:3:002:4 in terms of a mole ratio. Anisole wasused so that a concentration of methyl methacrylate in the solution forpolymerization was 50 wt %.

A compound (23)/methyl methacrylate/L-(−)-sparteine/anisole solution andcuprous bromide each were separately introduced into a feed forked heatresistant glass-made ampoule in a draft which was cut off from a UV ray.Then, freezing vacuum deaeration (pressure: 1.0 Pa) was carried outthree times by means of the vacuum device equipped with an oil-sealedrotary pump while taking care so that both were not mixed. The siliconcompound/methyl methacrylate/L-(−)-sparteine/anisole solution was mixedwith cuprous bromide in the feed forked heat resistant glass-madeampoule while maintaining a state of vacuum, and then the ampoule wasquickly sealed by means of a hand burner.

<Polymerization>

The sealed heat resistant glass-made ampoule was set in a constanttemperature shaking bath, and polymerization was carried out to obtain abrown viscous solution of a polymer (4a). In this case, thepolymerization temperature was 70° C., and the polymerization time was 2hours. The monomer conversion rate and a molecular weight and amolecular weight distribution of the polymer (4a) were determined in thesame manner as in Example 31, and the results thereof are shown in Table5.

EXAMPLE 49

Polymerization was carried out in the same manner as in Example 48 toobtain a brown viscous solution of a polymer (4b), except that thepolymerization time was changed to 4 hours. The monomer conversion rateand a molecular weight and a molecular weight distribution of thepolymer (4b) were determined in the same manner as in Example 31, andthe results thereof are shown Table 5.

TABLE 5 Conversion Number average Dispersion Example Polymer ratemolecular weight degree No. No. (mole-%) (Mn) (Mw/Mn) 39 3a 10.1 2,6001.10 40 3b 14.4 4,700 1.08 41 3c 16.6 6,500 1.07 42 3d 22.8 10,900 1.0743 3e 27.9 13,200 1.08 44 3f 39.9 18,400 1.10 45 3g 34.7 13,500 1.07 463h 52.8 20,500 1.09 47 3i 59.5 26,500 1.08 48 4a 18.4 6,600 1.08 49 4b23.2 8,200 1.08

EXAMPLE 50

<Preparation of Solution for Polymerization>

In this example, a proportion of the compound (23), methyl methacrylate,cuprous bromide and L-(−)-sparteine in the solution for polymerizationwas set in this order to 1:500:0.5:1 in terms of a mole ratio. Anisolewas used so that a concentration of methyl methacrylate in the solutionfor polymerization was 50 wt %.

A compound (23)/methyl methacrylate/L-(−)-sparteine/anisole solution andcuprous bromide were separately introduced into a feed forked heatresistant glass-made ampoule in a draft which was cut off from a UV ray.Then, freezing vacuum deaeration (pressure: 1.0 Pa) was carried out bymeans of the vacuum device equipped with an oil-sealed rotary pump whiletaking care so that both were not mixed. The frozen solution was moltenat a room temperature, and then dry argon gas was filled therein. Theoperation of carrying out freezing vacuum deaeration and filling ofargon gas was repeated three times in total, and then the compound(23)/methyl methacrylate/L-(−)-sparteine/anisole solution was mixed withcuprous bromide in the feed forked heat resistant glass-made ampoulewhile maintaining a state of filling argon, followed by quickly sealingthe ampoule by means of a hand burner.

<Polymerization and Analysis>

The sealed heat resistant glass-made ampoule was set in a constanttemperature shaking bath, and polymerization was carried out to obtain abrown viscous solution of a polymer (5a). In this case, thepolymerization temperature was 70° C., and the polymerization time was 2hours. A molecular weight and a molecular weight distribution of thepolymer (5a) were determined in the same manner as in Example 31, andthe results thereof are shown in Table 6. Further, a heat decompositiontemperature of the polymer (5a) was determined, and the result thereofis shown in Table 6.

EXAMPLE 51

Polymerization was carried out in the same manner as in Example 50 toobtain a solution of a polymer (5b), except that in this example, aproportion of the compound (23), methyl methacrylate, cuprous bromideand L-(−)-sparteine in the solution for polymerization was set in thisorder to 1:500:1:2 l in terms of a mole ratio and that thepolymerization time was changed to 2 hours. A molecular weight and amolecular weight distribution of the polymer (5b) were determined in thesame manner as in Example 31, and the results thereof are shown in Table6. Further, a glass transition point and a heat decompositiontemperature of the polymer (5b) were determined, and the results thereofare shown in Table 6.

EXAMPLE 52

<Preparation of Solution for Polymerization>

In this example, a proportion of the compound (23), methyl methacrylate,cuprous bromide and L-(−)-sparteine in the solution for polymerizationwas set in this order to 1:500:2:4 in terms of a mole ratio. Anisole wasused so that a concentration of methyl methacrylate in the solution forpolymerization was 50 wt %.

A compound (23)/methyl methacrylate/L-(−)-sparteine/anisole solution andcuprous bromide each were separately introduced into a feed forked heatresistant glass-made ampoule in a draft which was cut off from a UV ray.Then, freezing vacuum deaeration (pressure: 1.0 Pa) was carried outthree times by means of the vacuum device equipped with an oil-sealedrotary pump while taking care so that both were not mixed. The siliconcompound/methyl methacrylate/L-(−)-sparteine/anisole solution was mixedwith cuprous bromide in the feed forked heat resistant glass-madeampoule while maintaining a state of vacuum, and then the ampoule wasquickly sealed by means of a hand burner.

<Polymerization and Analysis>

The sealed heat resistant glass-made ampoule was set in a constanttemperature shaking bath, and polymerization was carried out to obtain abrown viscous solution of a polymer (6a). In this case, thepolymerization temperature was 70° C., and the polymerization time was 2hours. The monomer conversion rate and a molecular weight and amolecular weight distribution of the polymer (6a) were determined in thesame manner as in Example 31, and the results thereof are shown in Table6. Further, a heat decomposition temperature of the polymer (6a) wasdetermined, and the result thereof is shown in Table 6.

EXAMPLE 53

Polymerization was carried out in the same manner as in Example 52 toobtain a brown viscous solution of a polymer (6b), except that thepolymerization time was changed to 3 hours. The monomer conversion rateand a molecular weight and a molecular weight distribution of thepolymer (6b) were determined in the same manner as in Example 31, andthe results thereof are shown Table 6. Further, a glass transitiontemperature and a heat decomposition temperature of the polymer (5b)were determined, and the results thereof are shown in Table 6.

EXAMPLE 54

Polymerization was carried out in the same manner as in Example 52 toobtain a brown viscous solution of a polymer (6c), except that thepolymerization time was changed to 4 hours. The monomer conversion rateand a molecular weight, a molecular weight distribution, a glasstransition temperature and a heat decomposition temperature of thepolymer (6c) were determined in the same manner as described above, andthe results thereof are shown Table 6.

EXAMPLE 55

Polymerization was carried out in the same manner as in Example 52 toobtain a brown viscous solution of a polymer (6d), except that thepolymerization time was changed to 0.5 hour. The monomer conversion rateand a molecular weight, a molecular weight distribution, a glasstransition temperature and a heat decomposition temperature of thepolymer (6d) were determined in the same manner as described above, andthe results thereof are shown Table 6.

EXAMPLE 56

Polymerization was carried out in the same manner as in Example 52 toobtain a brown viscous solution of a polymer (6e), except that thepolymerization time was changed to 1.5 hour. The monomer conversion rateand a molecular weight, a molecular weight distribution, a glasstransition temperature and a heat decomposition temperature of thepolymer (6e) were determined in the same manner as described above, andthe results thereof are shown Table 6.

EXAMPLE 57

<Preparation of Solution for Polymerization and Polymerization>

Polymerization was carried out in the same manner as in Example 57 toobtain a brown viscous solution of a polymer (6f), except that thepolymerization time was changed to 2.5 hours. A molecular weight, amolecular weight distribution, a glass transition temperature and a heatdecomposition temperature of the polymer (6f) were determined in thesame manner as described above, and the results thereof are shown Table6.

EXAMPLE 58

<Preparation of Solution for Polymerization and Polymerization>

Polymerization was carried out in the same manner as in Example 52 toobtain a brown viscous solution of a polymer (6 g), except that thepolymerization time was changed to 2.1 hours. The monomer conversionrate and a molecular weight, a molecular weight distribution, a glasstransition temperature and a heat decomposition temperature of thepolymer (6 g) were determined in the same manner as described above, andthe results thereof are shown Table 6.

EXAMPLE 59

Polymerization was carried out in the same manner as in Example 52 toobtain a brown viscous solution of a polymer (6h), except that thepolymerization time was changed to 3.5 hours. The monomer conversionrate and a molecular weight, a molecular weight distribution, a glasstransition temperature and a heat decomposition temperature of thepolymer (6 h) were determined in the same manner as described above, andthe results thereof are shown Table 6.

EXAMPLE 60

Polymerization was carried out in the same manner as in Example 52 toobtain a brown viscous solution of a polymer (6i), except that thepolymerization time was changed to 5.5 hours. The monomer conversionrate and a molecular weight, a molecular weight distribution, a glasstransition temperature and a heat decomposition temperature of thepolymer (6i) were determined in the same manner as described above, andthe results thereof are shown Table 6.

EXAMPLE 61

Polymerization was carried out in the same manner as in Example 52 toobtain a brown viscous solution of a polymer (6j), except that thepolymerization time was changed to 7.0 hours. The monomer conversionrate and a molecular weight, a molecular weight distribution, a glasstransition temperature and a heat decomposition temperature of thepolymer (6j) were determined in the same manner as described above, andthe results thereof are shown Table 6.

TABLE 6 Dispersion Polymer Polymerization Conversion degree Tg TdExample No. No. time (hr) rate (mol-%) Mn (Mw/Mn) (° C.) (° C.) 50 5a 2— 2,700 1.09 — 394 51 5b 2 — 3,400 1.09 111 379 52 6a 2 17 10,300 1.07 —375 53 6b 3 23 13,400 1.09 106 349 54 6c 4 34 21,300 1.11 111 353 55 6d0.5  7 3,300 1.11 107 392 56 6e 1.5 10 5,000 1.10 109 389 57 6f 2.5 —6,700 1.07 108 373 58 6g 2.1 13 7,600 1.09 108 370 59 6h 3.5 20 11,8001.07  98 363 60 6i 5.5 30 19,400 1.05 110 360 61 6j 7 52 33,300 1.10 112342

Polymers can be obtained according to the examples described above byusing the compounds (24) to (29) in place of the compound (23).

COMPARATIVE EXAMPLE 1

In this comparative example, a proportion of p-toluenesulfonyl chloride,methyl methacrylate, cuprous bromide and L-(−)-sparteine in the solutionfor polymerization was set in this order to 1:200:2:4 in terms of a moleratio. Diphenyl ether was used so that a concentration of methylmethacrylate in the solution for polymerization was 50 wt %.

A p-toluenesulfonyl chloride/methylmethacrylate/L-(−)-sparteine/diphenyl ether solution and cuprous bromideeach were separately introduced into a feed forked heat resistantglass-made ampoule in a draft which was cut off from a UV ray. Then,freezing vacuum deaeration (pressure: 1.0 Pa) was carried out threetimes by means of the vacuum device equipped with an oil-sealed rotarypump while taking care so that both were not mixed. Thep-toluenesulfonyl chloride/methyl methacrylate/L-(−)-sparteine/diphenylether solution was mixed with cuprous bromide in the feed forked heatresistant glass-made ampoule while maintaining a state of vacuum, andthen the ampoule was quickly sealed by means of a hand burner.

<Polymerization and Analysis>

The sealed heat resistant glass-made ampoule was set in a constanttemperature shaking bath, and polymerization was carried out to obtain abrown viscous solution of a polymer (8a). In this case, thepolymerization temperature was 70° C., and the polymerization time was15 minutes. A molecular weight, a molecular weight distribution and aheat decomposition temperature of the polymer (8a) were determined inthe same manner as described above, and the results thereof are shown inTable 7.

COMPARATIVE EXAMPLE 2

Polymerization was carried out in the same manner as in ComparativeExample 1 to obtain a brown viscous solution of a polymer (8b), exceptthat the polymerization time was changed to 1 hour. A molecular weight,a molecular weight distribution, a glass transition temperature and aheat decomposition temperature of the polymer (8b) were determined inthe same manner as described above, and the results thereof are shownTable 7.

COMPARATIVE EXAMPLE 3

Polymerization was carried out in the same manner as in ComparativeExample 1 to obtain a brown viscous solution of a polymer (8c), exceptthat the polymerization time was changed to 2 hours. A molecular weight,a molecular weight distribution, a glass transition temperature and aheat decomposition temperature of the polymer (8c) were determined inthe same manner as described above, and the results thereof are shownTable 7.

COMPARATIVE EXAMPLE 4

Polymerization was carried out in the same manner as in ComparativeExample 1 to obtain a brown viscous solution of a polymer (8d), exceptthat the polymerization time was changed to 5 hours. A molecular weight,a molecular weight distribution, a glass transition temperature and aheat decomposition temperature of the polymer (8d) were determined inthe same manner as described above, and the results thereof areshown-Table 7.

COMPARATIVE EXAMPLE 5

Polymerization was carried out in the same manner as in ComparativeExample 1 to obtain a brown viscous solution of a polymer (8e), exceptthat in this comparative example, a proportion of p-toluenesulfonylchloride, methyl methacrylate, cuprous bromide and L-(−)-sparteine inthe solution for polymerization was set in this order to 1:200:1:2 interms of a mole ratio and that the polymerization time was changed to 4hours. A molecular weight, a molecular weight distribution, a glasstransition temperature and a heat decomposition temperature of thepolymer (8e) were determined in the same manner as described above, andthe results thereof are shown Table 7.

COMPARATIVE EXAMPLE 6

Polymerization was carried out in the same manner as in ComparativeExample 5 to obtain a brown viscous solution of a polymer (8f), exceptthat the polymerization time was changed to 5.5 hours. A molecularweight, a molecular weight distribution, a glass transition temperatureand a heat decomposition temperature of the polymer (8f) were determinedin the same manner as described above, and the results thereof are shownTable 7.

COMPARATIVE EXAMPLE 7

Polymerization was carried out in the same manner as in ComparativeExample 1 to obtain a solution of a polymer (8g), except that in thiscomparative example, a proportion of p-toluenesulfonyl chloride, methylmethacrylate, cuprous bromide and L-(−)-sparteine in the solution forpolymerization was set in this order to 1:500:2:4 in terms of a moleratio and that the polymerization time was changed to 6.3 hours. Amolecular weight, a molecular weight distribution, a glass transitiontemperature and a heat decomposition temperature of the polymer (8g)were determined in the same manner as described above, and the resultsthereof are shown Table 7.

TABLE 7 Polymeriza- Dispersion Comparative Polymer tion degree Tg TdExample No. No. time (hr) Mn (Mw/Mn) (° C.) (° C.) 1 8a 0.25 1,300 1.09— 381 2 8b 1 2,400 1.09  90 362 3 8c 2 4,400 1.10  99 353 4 8d 5 6,7001.05 104 354 5 8e 4 8,300 1.06 112 350 6 8f 5.5 13,600 1.10 105 345 7 8g6.3 30,300 1.16 110 352

In comparison of the polymers having almost the same molecular weights,the polymers obtained by using the compound (23) as the initiator show ahigher heat decomposition temperature excluding the case of the polymershaving a large molecular weight.

INDUSTRIAL APPLICABILITY

The silicon compound provided by the present invention is asilsesquioxane derivative having an excellent living polymerizableradical polymerization initiating function, and it is expected to revealcharacteristics which are completely different from those ofconventional silsesquioxanes. For example, it is possible to commencepolymerization by allowing and acryl base monomer to coexist to form anacryl base polymer making use of one point of the structure of thesilsesquioxane in the present invention as a starting point. In thepolymer thus obtained having an organic group of a silsesquioxanestructure at an end thereof, it is possible as well to positively makeuse of interaction between the organic groups of the silsesquioxanestructure thereof. This makes it possible to not only provide anorganic-inorganic composite material having a clear structure but alsocontrol the structure of this polymer as molecular assemblies. Inaddition thereto, the silicon compound of the present invention hasfurther characteristics other than a function as a polymerizationinitiator. For example, a halogenated sulfonyl group has a strongelectrophilicity, and therefore it is possible to synthesize varioussilsesquioxane derivatives by reacting the silicon compound of thepresent invention with various nucleophilic reagents. Accordingly, theabove compound can actively be used as an intermediate useful fororganic synthesis.

1. A silicon compound represented by Formula (1):

in Formula (1), seven R¹'s are groups independently selectedrespectively from the group consisting of hydrogen, alkyl, substitutedor non-substituted aryl and substituted or non-substituted arylalkyl; A¹is an organic group substituted with a halogenated sulfonyl group; inthe alkyl group, hydrogen may be optionally replaced by fluorine, and—CH₂— may be optionally replaced by —O—, —CH═CH—, cycloalkylene orcycloalkenylene; and in the alkylene moiety of the arylalkyl group,hydrogen may be optionally replaced by fluorine, and —CH₂— may beoptionally replaced by —O— or —CH═CH—.
 2. The silicon compound asdescribed in claim 1, wherein seven R¹'s in Formula (1) are groupsindependently selected respectively from the group consisting ofhydrogen, alkyl having a carbon number of 1 to 45, substituted ornon-substituted aryl and substituted or non-substituted arylalkyl; inthe alkyl group having a carbon number of 1 to 45, hydrogen may beoptionally replaced by fluorine, and —CH₂— may be optionally replaced by—O—, —CH═CH—, cycloalkylene or cycloalkenylene; and in the alkylenemoiety of the arylalkyl group, hydrogen may be optionally replaced byfluorine, and —CH₂— may be optionally replaced by —O— or —CH═CH—.
 3. Thesilicon compound as described in claim 1, wherein seven R¹'s in Formula(1) are groups independently selected respectively from the groupconsisting of hydrogen and alkyl having a carbon number of 1 to 30; andin the alkyl group having a carbon number of 1 to 30, hydrogen may beoptionally replaced by fluorine, and —CH₂— may be optionally replaced by—O— or cycloalkylene.
 4. The silicon compound as described in claim 1,wherein seven R¹'s in Formula (1) are groups independently selectedrespectively from the group consisting of alkenyl having a carbon numberof 1 to 20 and a group in which —CH₂— is optionally replaced bycycloalkenylene in alkyl having a carbon number of 1 to 20; in thealkenyl having a carbon number of 1 to 20, hydrogen may be optionallyreplaced by fluorine, and —CH₂— may be optionally replaced by —O— orcycloalkylene; and in the group in which —CH₂— is optionally replaced bycycloalkenylene in alkyl having a carbon number of 1 to 20, hydrogen maybe optionally replaced by fluorine.
 5. The silicon compound as describedin claim 1, wherein seven R¹'s in Formula (1) are groups independentlyselected respectively from the group consisting of naphthyl and phenylin which hydrogen may be optionally replaced by halogen or alkyl havinga carbon number of 1 to 10; in the alkyl group having a carbon number of1 to 10, hydrogen may be optionally replaced by fluorine, and —CH₂— maybe optionally replaced by —O—, —CH═CH—, cycloalkylene or phenylene. 6.The silicon compound as described in claim 1, wherein seven R¹'s inFormula (1) are groups independently selected respectively from thegroup consisting of phenylalkyls in which hydrogen on a benzene ring maybe optionally replaced by halogen or alkyl having a carbon number of 1to 12; in the alkyl group having a carbon number of 1 to 12, hydrogenmay be optionally replaced by fluorine, and —CH₂— may be optionallyreplaced by —O—, —CH═CH—, cycloalkylene or phenylene; and in thealkylene moiety of the phenylalkyl group, which has a carbon number of 1to 12, hydrogen may be optionally replaced by fluorine, and —CH₂— may beoptionally replaced by —O— or —CH═CH—.
 7. The silicon compound asdescribed in claim 1, wherein seven R¹'s in Formula (1) are groupsindependently selected respectively from the group consisting of alkylhaving a carbon number of 1 to 8, phenyl, non-substituted naphthyl andphenylalkyl; in the alkyl aroup having 1 to 8 carbon atoms, hydrogen maybe optionally replaced by fluorine, and —CH₂— may be optionally replacedby —O—, —CH═CH—, cycloalkylene or cycloalkenylene; in the phenyl,hydrogen may be optionally replaced by halogen, methyl or methoxy; inphenyl in the phenylalkyl group, hydrogen may be optionally replaced byfluorine, alkyl having a carbon number of 1 to 4, ethenyl or methoxy;the alkylene moiety of the phenylalkyl group has a carbon number of 1 to8, and —CH₂— in the alkylene moiety may be optionally replaced by —O— or—CH═CH—.
 8. The silicon compound as described in claim 1, wherein sevenR¹'s in Formula (1) are one group selected from the group consisting ofalkyl having a carbon number of 1 to 8, phenyl, non-substituted naphthyland phenylalkyl; in the alkyl having a carbon number of 1 to 8, hydrogenmay be optionally replaced by fluorine, and —CH₂— may be optionallyreplaced by —O—, —CH═CH—, cycloalkylene or cycloalkenylene; in thephenyl, hydrogen may be optionally replaced by halogen, methyl ormethoxy; in phenyl in the phenylalkyl group, hydrogen may be optionallyreplaced by fluorine, alkyl having a carbon number of 1 to 4, ethenyl ormethoxy; the alkylene moiety of the phenylalkyl group has a carbonnumber of 1 to 8, and —CH₂—in the alkylene moiety may be optionallyreplaced by —O— or —CH═CH—.
 9. The silicon compound as described inclaim 1, wherein seven R¹'s in Formula (1) are one group selected fromthe group consisting of phenyl, naphthyl and phenylalkyl; in the phenyl,hydrogen may be optionally replaced by halogen, methyl or methoxy; inphenyl in the phenylalkyl group, hydrogen may be optionally replaced byfluorine, alkyl having a carbon number of 1 to 4, ethenyl or methoxy;the alkylene moiety of the phenylalkyl group has a carbon number of 1 to8, and —CH₂— in the alkylene moiety may be optionally replaced by —O—.10. The silicon compound as described in claim 1, wherein seven R¹'s inFormula (1) are ethyl, 2-methylpropyl, 2,4,4-trimethylpentyl,3,3,3-trifluoropropyl, cyclopentyl, cyclohexyl or non-substitutedphenyl.
 11. The silicon compound as described in claim 1, wherein sevenR¹'s in Formula (1) are non-substituted phenyl.
 12. The silicon compoundas described in any of claims 1 to 11, wherein A¹ in Formula (1)described in claim 1 is a group represented by Formula (2):

in Formula (2), X is halogen; R² is alkyl having a carbon number of 1 to3; a is an integer of 0 to 2; Z¹ is a single bond or alkylene having acarbon number of 1 to 10; in the alkylene having a carbon number of 1 to10, —CH₂— may be optionally replaced by —O—, —COO— or —OCO—; and both ofthe bonding positions of halogenated sulfonyl and R² on the benzene ringare optional positions.
 13. The silicon compound as described in claim12, wherein Z¹ in Formula (2) is Z²—C₂H_(□)—; Z² is a single bond,oralkylene having a carbon number of 1 to 8, and —CH₂— in the alkylenegroup may be optionally replaced by —O—, —COO— or —OCO—.
 14. The siliconcompound as described in claim 12, wherein in Formula (2), Z¹ is —C₂H₄—;X is chlorine or bromine; and a is
 0. 15. A production process for thesilicon compound represented by Formula (1) as described in claim 1,which comprises reacting a compound represented by Formula (3) withtrichlorosilane having a halogenated sulfonyl group:

in Formula (3), seven R¹'s are groups independently selectedrespectively from the group consisting of hydrogen, alkyl, substitutedor non-substituted aryl and substituted or non-substituted arylalkyl; inthe alkyl group, hydrogen may be optionally replaced by fluorine, and—CH₂— may be optionally replaced by —O—, —CH═CH—, cycloalkylene orcycloalkenylene; and in the alkylene moiety of the arylalkyl group,hydrogen may be optionally replaced by fluorine, and —CH₂— may beoptionally replaced by —O— or —CH═CH—.
 16. A production process for asilicon compound represented by Formula (5), which comprises reacting acompound represented by Formula (3) with a compound represented byFormula (4):

wherein R¹ in Formula (3) is one group selected from the groupconsisting of alkyl having a carbon number of 1 to 8, phenyl,non-substituted naphthyl and phenylalkyl; in the alkyl group having acarbon number of 1 to 8, hydrogen may be optionally replaced byfluorine, and —CH₂— may be optionally replaced by —O—, —CH═CH—,cycloalkylene or cycloalkenylene; hydrogen in the phenyl may beoptionally replaced by halogen, methyl or methoxy; in the phenylalkyl,hydrogen on a benzene ring may be optionally replaced by fluorine, alkylhaving a carbon number of 1 to 4, ethenyl or methoxy, and —CH₂— in thealkylene moiety may be optionally replaced by —O—; R¹ in Formula (5) hasthe same meaning as that of R¹ in Formula (3); in Formula (4), X ishalogen; R² is alkyl having a carbon number of 1 to 3; a is an integerof 0 to 2; Z² is a single bond or alkylene having 1 to 8 carbon atoms;in the alkylene group having a carbon number of 1 to 8, —CH₂— may beoptionally replaced by —O—, —COO— or —OCO—; both of the bondingpositions of halogenated sulfonyl and R² on the benzene ring areoptional positions; and the meanings of X, R², and Z² in Formula (5) andthe bonding positions of halogenated sulfonyl and R² on the benzene ringare the same as those in Formula (4).
 17. A production process for thesilicon compound represented by Formula (1) as described in claim 1,which comprises reacting a compound represented by Formula (6) withtrichiorosilane having a halogenated sulfonyl group:

in Formula (6), seven R¹'s are groups independently selectedrespectively from the group consisting of hydrogen, alkyl, substitutedor non-substituted aryl and substituted or non-substituted arylalkyl; Mis a monovalent alkali metal atom; in the alkyl group, hydrogen may beoptionally replaced by fluorine, and —CH₂—may be optionally replaced by—O—, —CH═CH—, cycloalkylene or cycloalkenylene; and in the alkylenemoiety of the arylalkyl group, hydrogen may be optionally replaced byfluorine, and —CH₂— may be optionally replaced by —O— or —CH═CH—.
 18. Aproduction process for a silicon compound represented by Formula (5),which comprises reacting a compound represented by Formula (6) with acompound represented by Formula (4):

in Formula (6), R¹ is one group selected from the group consisting ofalkyl having a carbon number of 1 to 8, phenyl, non-substituted naphthyland phenylalkyl; M is a monovalent alkali metal atom; in the alkyl grouphaving a carbon number of 1 to 8, hydrogen may be optionally replaced byfluorine, and —CH₂— may be optionally replaced by —O—, —CH═CH—,cycloalkylene or cycloalkenylene; hydrogen in the phenyl may beoptionally replaced by halogen, methyl or methoxy; in the phenylalkylgroup, hydrogen on a benzene ring may be optionally replaced byfluorine, alkyl having 1 to 4 carbon atoms, ethenyl or methoxy, and—CH₂—in the alkylene moiety may be optionally replaced by —O—; R¹ inFormula (5) has the same meaning as that of R¹ in Formula (6); inFormula (4), X is halogen; R² is alkyl having 1 to 3 carbon atoms; a isan integer of 0 to 2; Z² is a single bond or alkylene having a carbonnumber of 1 to 8; in the alkylene group having a carbon number of 1 to8, —CH₂— may be optionally replaced by —O—, —COO— or —OCO—; both of thebonding positions of halogenated sulfonyl and R² on the benzene ring areoptional positions; and the meanings of X, R², and Z² in Formula (5) andthe bonding positions of halogenated sulfonyl and R² on the benzene ringare the same as those in Formula (4).
 19. A polymer obtained bypolymerizing a vinyl base monomer using the silicon compound representedby Formula (1) as described in claim 1 as an initiator and a transitionmetal complex as a catalyst.
 20. A polymer represented by Formula (7)obtained by polymerizing a vinyl base monomer using the silicon compoundrepresented by Formula (1) as described in claim 18 as an initiator anda transition metal complex as a catalyst:

the meanings of R¹, Z², R², a and X in Formula (7) and the bondingpositions of halogenated sulfonyl and R² on the benzene ring are thesame as those in Formula (6) as described in claim 18, and P is a vinylbase polymer.
 21. The polymer as described in claim 19 or 20, whereinthe vinyl base monomer is at least one selected from the groupconsisting of a (meth)acrylic acid derivative and a styrene derivative.22. The polymer as described in claim 19 or 20, wherein the vinyl basemonomer is at least one selected from the group consisting of the(meth)acrylic acid derivatives.
 23. A polymerization process for a vinylbase monomer which comprises using the silicon compound represented byFormula (1) as described in claim 1 as an initiator and using atransition metal complex as a catalyst.
 24. A production process for thepolymer represented by Formula (7):

the meanings of R¹, Z², R², a and X in Formula (7) and the bondingpositions of halogenated sulfonyl and R² on the benzene ring are thesame as those in Formula (6) as described in claim 18, and P is a vinylbase polymer, which comprises polymerizing a vinyl base monomer usingthe compound represented by Formula (5) as described in claim 18 as aninitiator and using a transition metal complex as a catalyst.